Vega from the Street Fighter series is a narcissistic ninja bullfighter aristocrat whose hobbies include carving people up with a clawed gauntlet in order to watch their blood pool beneath them, likening it to a blooming rose. Though he finds it vulgar when it sprays.
Thankfully, he is kind towards his opponents, and even compliments the beauty of his opponents (Chun-Li & Cammy being the most common ones).
Juri is an Ax-Crazy murderer with "rules" and "boring people" in the "dislikes" portion of her profile. Even Sakura isn't afraid to call out Juri with her obsession with deathmatches.
Dio from World Heroes 2 is a Humanoid Abomination created by the Mad ScientistDr. Damundo. After the defeat of his previous creation, Geegus, he made a much more powerful one, which decided to abandon the doctor and destroy the world by itself, killing millions of innocent people. After Geegus is defeated, Dio comes from nowhere and challenges the protagonist, intending to kill anyone who interferes in his plans.
Ultimate Proto-Bot 10000 from Club Penguin is indeed the most dangerous villain in the game. Unlike Herbert, he wants to permanently destroy the EPF instead of just defeating them, and he's shown to be crueler, more wicked and more arrogant than the former while doing just what he wants like ruling places without intending to make fair rules. He also used to have a will of ruling all of Club Penguin Island, but in later parties he started wanting to destroy the entire galaxy. His lack of respect for rules is also apparent in the minigame System Defender where he adapts his attacks to the player's defenses (or tries to) instead of letting the entire battle be formularic like the other levels.
Darth Malak is a lunatic that does nothing but throw the endless fleet the Star Forge provides him with at the enemy, and he lives up to that, since the first time we see him, he orders an orbital bombardment to level an entire planet just because he was impatient about his army's progress with looking for one Jedi. His relentless Stupid Evil serves to make him more threatening, as the Player Character is the only thing stopping him from nuking the galaxy into a new dark age.
Darth Nihilus from the sequel is an Omnicidal Maniac who seeks to devour all life in the galaxy so that he can sate his hunger. His associate Darth Sion isn't much better, as his only real goal is to kill every Jedi he can find so he can do whatever he wants unopposed.
Eventually, everyone who plays Grand Theft Auto gets powerful and bored/pissed off enough that they become this. Ditto any other crime sandbox game. Protagonist-wise, Trevor Phillips of Grand Theft Auto V is the closest to this and is stated to be inspired by the mindset of said players.
Black Whirlwind from Jade Empire, an Ax-Crazy mercenary whose chaotic and impulsive actions (sleeping with his employer's wife, cutting a girl two rivals were fighting over in half) normally end in him having to kill everyone in self defense.
Albert Wesker. By Resident Evil 5, he hates everyone in the world and seeks to genocide the human race. Plus half the things he did beforehand, from taking a preteen outbreak survivor prisoner to injecting Jill with viruses and forcing her to aid him just so she can suffer.
Anything infected with the T-Virus. No matter how harmless or non-violent it was before, no matter the intelligence it has after (Some of them are quite smart), be it man, animal, vegetable, or mineral, you'd better believe it lives only to sow death and destruction once infected.
Tira, Cervantes, and Nightmare in Soul Series. Soul Edge has rendered them all insane killing machines with little regard for who's on the other side of the blade.
Kefka of Final Fantasy VI, an Ax-Crazy, OmnicidalMonster Clown and a Chaotic Evil hybrid of types 2 and 4. In the first part of the game he works for The Empire, but disobeys orders whenever he feels like it so he can, for example, gleefully slaughter a city and hear the people scream. In the second part he is a Physical God and rules over the world... Or rather, the scraps and ruins of it that are left.
Luca Blight from Suikoden II. He murdered his own troops (specifically, the youth brigade, composed of teenagers) and pinned the blame on the opposing side in order to put an end to a peace treaty, razed entire villages full of civilians, executed those who begged for their lives, attempted to cut a little girl in half while wearing a sinister grin on his face, assassinated his own father in order to become king, slaughtered the entire population of Muse in order to power-up a True Rune, pursued unarmed refugees and killed them... The list goes on and on.
A chaotic evil character alignment is possible in Infamous, just like in all sandbox games. Infamous is made distinct by the fact that the player has the option to choose their character alignment through their actions, and character alignment is actually a major element in the way that the game plays out. If you choose to be chaotic evil, then people will hate you, the city will descend deeper into crime and anarchy, and you will gain powers exclusive to evil characters.
Kerrigan from StarCraft once the Expansion PackBrood War rolls around. She plays The Chessmaster to get into power, and once there does whatever she feels like while massacring her remaining competition. She leaves Zeratul alive after forcing him to kill his Matriarch in order to free her, so that his "every waking moment will be torture." She also lampshades it by calling herself the "Queen Bitch of the universe."
Hell is depicted this way in the Diablo mythos. Its denizens enjoy slaughtering and corrupting mortals, and hold chaos as a cosmic ideal to which all reality should bend. However, besides the Three Prime Evils who rule Hell, most of the forces of Hell seem to in fact be Stupid Evil, and are perfectly willing to simply slaughter each other for all eternity.
The Fiends are a gang of savage, drug-addicted killers who terrorize the wasteland and cause mayhem wherever they go. Some of their leaders in particular put even Caesar's Legion to shame in terms of cruelty. They are also the only story-important faction in the game that the player cannot befriend (aside from selling them drugs).
The Courier ends up being this, if s/he decides to go the Wild Card route, but without upgrading to the securitrons, condemning the Mojave to chaos and death.
The Umgah from Star Control II are a race of practical jokers who seem to have little to no loyalty to anyone or anything, even attacking the player after he saves their entire race, just for kicks and giggles. The fact that the Umgah's pranks are implied to cause the death of thousands, if not millions of sentient beings puts them squarely in the "evil" category. For example, they drop miles-wide meteors into the oceans of inhabited planets and consider it hilarious.
The Kohr-Ah probably also qualify, as opposed to their Lawful Evil counterparts the Kzer-Za. The Kzer-Za believe that the key to their race's survival is to enslave everybody else, thus bringing order and hierarchy to the galaxy. The Kohr-Ah on the other hand believe that if there are no living sentient races, then they can never again be made slaves and kill. Anyone and everything that isn't them must die.
The Edel Bernal, the Big Bad and True Final Boss of Super Robot Wars Z is a perfect example of this alignment. He lives only for the pleasure of death and destruction and cause the dimensional collapse which resulted in the countless conflicts of the game for fun.
Bishop of Neverwinter Nights 2 is canonically a Type 3 Chaotic Evil human ranger. While not a sociopath, he is a major jerk, and will happily slaughter his way through anyone to achieve his goals. He firmly believes in Social Darwinism, that the concept of civilization and culture are a total sham, and that everyone, even (or perhaps especially) him, is just a rabid animal waiting to strike. He will also betray you during the siege on your fortress, claiming he is always on the winning side. It is possible to convince him later on not to attack you in the final battle of the game, though only if he likes/respects you enough..
The Postal Dude, and in fact, the Postal series embody this alignment. Basically the series is about doing whatever you feel like, which typically involves going postal against society.
Tales of Vesperia's Zagi may very well be the embodiment of this alignment. Not only is he Ax-Crazy to the nth degree, about 90% of his dialogue is either him giving an over the top Evil Laugh or a deranged non sequitur. To specify, he starts out as a Psycho for Hire, but gradually becomes a Stalker with a Crush towards Yuri and indulges in Cybernetics Eat Your Soul just so he can have the satisfaction of defeating and killing him. It takes no less than five battles to finally defeat him. "Hahahaha! I'm gonna kill you and carve your name into my blood!"
The Legend of Zelda: Majora's Mask has the Eldritch Abomination Majora. Its host Skull Kid started out as merely a lonely kid who didn't know how to get attention other than pranks. After Majora possessed and corrupted him through the Evil Mask, Skull Kid turned to seeking attention by playing gruesome, often lethal "games" with the population of Termina. When you actually fight Majora itself, it acts more like a Psychopathic Manchild than anything else. This thing makes Ganondorf look friendly by comparison.
Dark Star/Dark Bowser from Mario & Luigi: Bowser's Inside Story. There's a good reason it's a Sealed Evil in a Can in the first place, that being that it's completely omnicidal without a cause (as in, wants to destroy the entire world and everything in it bar maybe itself). It also clones others via copying their DNA, which is... bad news when it gets eaten by Bowser.
"Soon this kingdom will vanish along with all who dwell within. And you, too, will sleep eternally in the dark power's embrace!"
Shiro Tagachi from Guild Wars. He's bent on destroying the entire continent of Cantha (hence the Jade Wind) and actively seeks revenge the entire time he's "dead".
Persona 4 has the Killer, Tohru Adachi. He's a nihilistic asshole who murdered two people, duped the Second Suspect into taking up his murder attempts, and watched it all happen like a spectator at a ball game. His motivations boil down to him throwing a tantrum over his poor lot in life, lashing out over his Small Town Boredom, and his own amusement.
Gary Smith from Bully. After the first chapter of the game, he schemes behind the scenes, then sets his master plan into action in the last chapter. He causes a riot, ties up the head, gets several kids expelled (sending several more through therapy), does enormous amounts of vandalism and destruction, lies to everyone, and calls your mother a whore. Why? Because he can!
Zevran Arainai of Dragon Age: Origins is a rare example of a Chaotic Evil party member that's actually quite pleasant to be around, thanks to his wit and charm. He seems to mostly be a Type 1, given that freedom from the Antivan Crows is his primary concern, but he also shows little or no remorse for the lives he's taken up until that point. His original nature seemed to be leaning towards Chaotic Good, but his enforced service to the Crows over a lifetime has generally winnowed away any morality he had, especially a few seriously tragic events. He can be brought back to CG with a Romance, or at LEAST Chaotic Neutral with enough approval, though he's still an assassin by trade. Zevran shows up in one quest for the sequel, and is now firmly CN, as he's more or less started assassinating the other assassins rather then taking marks himself, mostly because they won't stop trying (and failing) to kill him. He appears to be insuring his freedom by single-handedly dismantling the entire Antivan Crows organization bit by bit.
Morrigan is also Chaotic Evil, leaning more towards Chaotic. She attaches great importance to personal freedom and disapproves of oppression throughout Thedas, but disapproves of any charitable acts and approves of some of your worst atrocities. It is notoriously difficult to play a Lawful Good type and still keep her approval high.
Sarevok Anchev and Amelyssan the Blackhearted, the Big Bads in Baldur's Gate and Baldur's Gate II: Throne of Bhaal, are both good examples of intelligent, patient Chaotic Evil, though both also show a bit of a fiery temper in the short term in spite of being Chessmasters. Both of their plans involve building alliances and beguiling everyone only to tear it all apart by having everyone kill everyone in an orgy of bloodshed so that they can have supreme power for themselves.
Bodhi is a predatory, sadistic and bloodthirsty vampire, intelligent but somewhat unrestrained, who was originally motivated by lust for godly power and is now driven by revenge.
The necromancer Xzar is somewhat sadistic, lacks any empathy and is completely, utterly unhinged, varying between coldly sarcastic and cheerfully (or otherwise) insane.
Tiax from the first game. A gnome thief/cleric of Cyric, Tiax is also totally insane, yelling to anyone who'll listen in a loud, over-the-top manner about how magnificent it will be once he rules the world — with an iron fist, naturally. It's a little telling that you can find him in Spellhold, an asylum for mad mages that functions more as a lock-up-people-we-don't-like facility, and no-one's upset that he's there.
Orin the Red from Baldur's Gate III is the psychotic and bloodthirsty chosen of Bhaal, who is only interested in butchering people to please her patron deity, in contrast to the Lawful Evil Enver Gortash who wants to rule the Sword Coast.
Gig from Soul Nomad & the World Eaters; brash, deceptive, impulsive, crude, attempts to solve all his long-term problems (mainly the one that there's people still alive on the same plane of existence as he) with simple short-term solutions (mainly killing everything in sight) and turned the protagonist's homeworld into a slowly dying dustbowl because he thinks wanton slaughter of mortals is fun. Oh yeah, and he's on your side, which turns the game into a rather interesting case of being the Kid with the Leash. Gig gets Character Development during the story and ends up more of a Chaotic NeutralThe Imp. The good ending to the Demon Path also sees him overcome his Laser-Guided Amnesia and return to his Lawful Good former incarnation.
The one guy who's worse than that: you, in the Demon Path, who decides to just go kill everyone because he or she felt like it. Oh, and Gig in that storyline? Eventually, you absorb him instead of the other way around if you win the final battle. Fun stuff.
While the leadership of the Burning Legion was firmly Lawful Evil, the individual demons that comprise its ranks mostly fell into this alignment, being creatures of pure chaos and inherently destructive overall. Your average imp or felguard dud not care much for Sargeras's grand plan of purifying the cosmos: they just wanted to smash things, kill people and sate their magic addiction. An example of a named Legion character of this alignment would be the pit lord Mannoroth: there was nothing complex about his motivations like with Kil'jaeden or Sargeras himself, just rage and the desire to sow chaos.
Deathwing the Destroyer, progenitor of the black dragonflight. The reason he first joined the Old Gods was to be free of his burden as the Dragon Aspect of Earth - which involved destroying said earth to free them in the process, but who carsd about that? He was a more reserved, manipulative character in his earlier appearances, but by the time of Cataclysm, he had fully become the archetypical chaotic evil villain: a violent force of nature which sowed destruction, seemingly at random, for no reason other than rage and hatred. For that matter, most of the more insane followers of the Old Gods fit into that category as well.
Sylvanas Windrunner, especially in Battle for Azeroth and onwards (prior to that she was more Chaotic Neutral). She's an unpredictable character - always scheming and plotting, but also prone to violent sadism and fits of rage - and seemingly has no other goal in her life than to remain alive and free, no matter the cost. She notably serves as a good contrast to Garrosh Hellscream, another evil Horde leader. Whereas Garrosh, as a Lawful Evil character, was a fanatic, keeping to orcish honour no matter how many would die to satisfy his hunger for war, Sylvanas voices her distaste for the concept, seeing it as a detriment to the success of the Horde and her own plans.
Jeremy from Wild ARMs 4 started out as Neutral Evil. However, when you face him for the last time, he's definitely descended into this alignment, mainly because [[spoiler:becoming part-ARM made him completely Ax-Crazy.
Most Daedra of The Elder Scrolls. Sheogorath is the quintessential and charming example, extremely powerful and more likely to send flaming pets raining down on a village as provide useful advice. The only rule he follows is that he won't make things more sane ...except when his curse de-activates. In reality, though, Sheogorath is more like a pendulum that swings between Chaotic Evil, Chaotic Neutral and Chaotic Good (he is the prince of madness, after all). On the one hand, he's a psychopath and Ax-Crazy, on the other hand he helped the Chimer (who later became the dark elves) move from Summerset Isle and form their pre-tribunal culture. He's also very keen on punishing those that deserve it, or teaching lessons to people. And he invented music.
Technically none of the Daedra qualify as their motives are so far above your head you can't comprehend it. If there were any, however, they would be Molag Bal, ''King of Rape''; Boethia, who has aspects of anarchy and Darwinism; Mehrunes Dagon, who wants nothing more than to tear down creation; Vaermina, who rules over dreams and whose purpose is to torture everyone she can with the most horrifying nightmares possible; and Mephala, whose aspect is purposely veiled from mortal interpretation, but all she/he ever does is cause destruction and sow chaos. She also might be the patron of both assassin's guilds and destroys peace for the sake of it. The ironic thing here is that Boethia and Mephala, alongside Azura, are considered the good Daedra! Of course, of the three, only Azura is looked upon kindly outside of Morrowind.
Goremand from Trials of Mana brainwashes two best friends of the main characters into attacking them and helps the Dark Lich gain control of the Mana Sword just for giggles.
Omega from the Mega Man Zero series fits here, being a bloodthirsty machine of destruction. However, he's only doing it because Dr. Weilreprogrammed him to do so - in actuality, Omega was supposed to be the last resort to protect both humans & Reploids. Once you reach his final phase, you can really see why X wanted Omega under lock and key.
Leon the Black Knight from Yggdra Union is a bloodthirsty, batshit insane warrior who thinks nothing of slaughtering anyone who crosses him. He's probably the most evil character, along with the Lawful Evil Mardym.
Morinth from Mass Effect 2 has a genetic condition that kills the people she has sex with, and spends her time manipulating people into adoring her, then kills them with said condition when she's bored of them. Once, she used Samara's Knight Templar code to force Samara to kill a village of people she'd brainwashed into worshipping her as a goddess.
Renegade Shepard sometimes shows signs of this. Unless roleplayed otherwise, the majority of his/her actions lean more towards Chaotic Neutral, but sometimes there are some renegade actions that have no real justification, such as urging a drug-addled civilian to throw himself at a band of mercenaries for shits and giggles, and manipulating Annoleis and Gianna into killing each other when they could have gotten what they wanted from them in a much more straight forward way.
Mass Effect 3 allows you to go on a team-killing rampage—Ashley/Kaiden, Legion, Mordin, and Wrex can all be put down by Shepard, depending on the choices made. However, Renegade Shepard here is far more Chaotic Neutral, even Chaotic Good in some places. A Renegade in Mass Effect 3 basically believes that sacrifice is necessary, while the Paragon wants to save everyone they can. Both have their flaws.
BlazBlue's Yuuki Terumi (a.k.a. Hazama) has, as his apparent overall plot, the desire to create the Kusanagi, the sword of the godslayer. To do this, he's performed almost every single atrocity that occurs in the game towards any of the other characters. And we mean everything. He fucked up Ragna's life by cutting off his arm and kidnapping his sister, fucked up Jin's life by giving him the sword that messed with his mind, fucked up Noel's life by turning her into the Kusanagi (though it is noteworthy that this ended up backfiring on Terumi due to Mu-12 turning good after realizing what she was made for, it's still not like anything had gone well for Noel before), fucked up Arakune's life by turning him into the monster he is, etc. He is nearly impossible to control or predict (partly due to his destructive impulses and partly due to his plans upon plans upon plans upon plans upon plans) and absolutely hates to receive orders. And thus far, his actions have mainly been For the Evulz. When Chronophantasma is revealed, it only takes to the end of the promoting trailer until he reveals his other goal which is also encompassed in Kusanagi: To Create a Playground for Evil where all humans kill each other while he just watches in amusement because that's what he considered entertaining. Needless to say, he's one of the more dangerous Type 4 Chaotic Evil characters with a bloodcurdling portion of Type 2 Neutral Evil thrown in for good meassure.
Dracula, the Big Bad of the Castlevania franchise. He turns to the psychotic mass murder of humans to avenge his beloved wife. In Castlevania: Dawn of Sorrow, Soma Cruz, who is normally Chaotic Good, could become this as well if he sees the same fate happening in front of his very eyes.
Vanitas from Kingdom Hearts: Birth by Sleep is supposed to be The Dragon to Master Xehanort, but it's made quite clear that he's a Dragon with an Agenda who only works for Xehanort because it allows him to do as much evil as he pleases. Justified given that he's made of nothing but darkness.
Constantine, the villain from Thief: The Dark Project wanted nothing less than causing the world to return to chaos.
Vaas from Far Cry 3 is a psychopath leading the pirates that occupy the game's setting of Rook island. Most conversations with him begin with uncanny attempts at pleasantness on his part which then proceed into violent death threats issued at the slightest provocation. Nowhere else is his madness more apparent than his infamous "definition of insanity speech".
Marx from Kirby Super Star tricks Kirby into summoning NOVA under the pretense of wishing for the sun and moon to stop fighting. In reality, it's so that Marx can wish to control Pop Star, allowing him to "cause all the mischief [he] wants".
Vladimir Makarov from Call of Duty attacks a Russian airport to get Russia to attack the US (which Shepherd exploited) and is shown to have no loyalty to the Ultranationalists, despite being one himself.
Raul Menendez from Call of Duty: Black Ops is a very charismatic version of Chaotic Evil, described as an anarchist whose main goal is toppling Western civilization in revenge for his family's death and leave it on equal ground with third-world nations, and is referred to as "Messiah of the 99%" by his loyal followers, who seek to end the corrupt reign of the 1%.
J. D. Thorne from Tron 2.0 has the dubious distinction of being the only true Chaotic Evil character in the TRON universe. The movie villains are Lawful Evil, the other villains in the game are Neutral Evil. Once Thorne is in the system and merged with The Corruption, all he cares about is his status as a "Master User" and corrupting more and more Programs and systems with his disease.
Shao Kahn. In the war between the realms of Order and Chaos, the forces of Chaos want to put Kahn back on the throne of Outworld, because under his rule the only law was "obey Shao Kahn" and he didn't really give a crap about what anyone else was doing. He promoted infighting and competition amongst his minions in a "divide and rule" policy to the point where the Centaur and Shokan races went to war with one another to curry his favour (and thus gain more power). While is goal is to merge all the realms with Outworld and rule over everything, it's an ambition based solely on ego and a lust for conquest and power, and as long as he holds absolute power he doesn't really care about how his people live their day to day lives, though it tends to be pretty miserable, desperate and violent thanks to how sadistic and brutish he is.
Havik from the Realm of Chaos is either this or Chaotic Neutral, in the sense that he promotes Chaos as an ideal throughout the realms and actively opposes the Realm of Order and its plans. In Armageddon both he and Hotaru, the Order champion, were on the side of Evil, though that's mostly because there wasn't a Order Versus Chaos thing going on.
Quan Chi. In Deadly Alliance both he and Shao Kahn are mentioned as using the Mortal Kombat tournament "to destroy all that is good", and in the earlier Mortal Kombat Gold he tells Baraka that his only goal is to obtain power...which apparently entails killing everyone everywhere so that he doesn't have to "hold coil" to them, ie. he thinks ultimate power, by definition, has to mean zero responsibility, and he'll kill them to ensure no one so much as tries to make him responsible for anything. And lets not get started on his Chronic Backstabbing Disorder.
In Deception, Kabal performs a Face–Heel Turn and reforms The Black Dragon as a Chaotic Evil organization out to cause global anarchy. Thanks to a Cosmic Retcon, this became an Aborted Arc and last time we saw him he was still a hero, a dead hero.
The Crusaders faction of the Resistance of Praetoria in City of Heroes fit this neatly. While the resistance as a whole is trying to overthrow the oppressive government — which will have dangers and consequences — the Crusaders' methods are monstrous, including blowing up hospitals to teach the populace that Emperor Cole can't protect them. Some Crusaders are Well Intentioned Extremists, but others just like destruction.
Mr. Scratch, the Big Bad of Alan Wake's American Nightmare, fits this alignment quite nicely. For reference, take a gander at his monologue before he tortures a man to death:
Mr. Scratch: This poor slob's just collateral damage, really. I mean, I beat some information out of him earlier. But this part? (Pulls off the man's tie.) This is just for kicks. (Begins choking him.)
Assault Bomber from Bomberman Generation is easily Chaotic Evil. He is overly obsessed with death and destruction and will do anything to achieve it. He is malevolent and EXTREMELY psychotic to the point of having no self-control whatsoever. His title is "the Reaper of the Crush Bombers" for a reason.
The Four Kings fall in the same spot as the Darkwraiths, being tempted by Kaathe to gather Humanity, leading to the fall of New Londo and their imprisonment in the Abyss.
In the DLC, Manus, the Father of the Abyss, is a devastating corrupting monster that caused the Abyss to go out of control and consume the township of Oolacile, which killed most of the population and turned the rest into mindless, murderous, and mutated abominations. Despite the near-apocalyptic levels of power he wields, his mind is completely and utterly shattered under the weight of his volatile humanity, leaving him as a raving madman. The beings he corrupts are just as unstable and insane, from the Bloatheads of Oolacile to Artorias the Abysswalker.
Ridley in the Metroid franchise is a bloodthirsty petrodactyl-like villain who revels in wreaking destruction across the galaxy, and is responsible for the murder of Samus' parents during his raid on her home planet. The Space Pirates make him their general due to his extremely evil nature and immense power.
The Xenon from the X-Universe series are a very hard Type 3. They are the descendants of the original Terraformers, a collection of highly advanced robots created by the Terrans to locate and colonize planets into habitability. In the 2140s, an idiotic programmer bungled a software patch and caused the Terraformers to go rogue and attempt to "terraform" all other life into extinction; only the brave and successful attempts of luring the now insane Terraformers to a gate and the subsequent destruction of it by a particular Terran task force (who would later become the Argons) saved the Terrans from extinction. The Xenon was born as a splinter group from the original Terraformers and view all organic life as prey fit for extinction.
Sliske in Runescape tries to turn the PC into a wright just because he thinks they would make a good addition to their collection, kills Guthix and tries to incite a second God War just to make things more interesting.
Irving from Gods Will Be Watching is a torturer who loves his job because it lets him hurt people all he wants and get paid for it. He works for the Holistic Empire because they don't believe in such things as equality or human rights, allowing the strong to rise on their own merits, and, again, because their lack of human rights means he gets to torture prisoners. He and his silent partner are the only unambiguously evil characters in a game full of Gray-and-Grey Morality.
The Pack from the Nuka World DLC of Fallout 4 lean towards this. Taking the feral concept of nature that only the toughest survive is largely their role. Howling, watching dog fights, and treating each other like animals makes them resemble an ancient tribe, particularly the more bloodthirsty kinds.
The Paranoid Incarnation in Planescape: Torment is canonically Chaotic Evil, and reading his memoirs explains a lot of it. Almost completely insane and extremely individualistic, he spent most of his life trying to come up with far-fetched scenarios to protect himself, murdering people who were trying to help him for being 'useless', and left a lot of traps and pain behind him to spite all the other Incarnations of The Nameless One for 'stealing his body'. Despite all this, it is entirely possible to feel pity for him when you finally meet, simply because he couldn't handle the torment inherent to being who he was.
Fire Emblem: Path of Radiance has the Big Bad Ashnard. In addition to being violently and malevolently insane, his ultimate goal is to use the power of the dark goddess to turn all of Tellius into a Social Darwinist anarchy where only power holds sway. He wouldn't look out of place in a Shin Megami Tensei game.
The Voices of Nerat, Archon of Secrets and leader of the Scarlet Chorus, is a Type 2 with shades of Type 4. He’s a cruel and sadistic Court Jester who loves to cause mayhem, encourages Klingon Promotion among his forces, and routinely asks the Player Character to send important allies his way so he can consume their minds. Despite his love of mayhem, he willingly serves Kyros and (in theory, at least) takes care never to truly piss off his liege. He is also a babbling lunatic who is well aware of his own insanity, as well as a brilliant schemer; if killed, it is mentioned in the epilogue that some of his former Mooks think He's Just Hiding
Verse, one of Nerat’s Elite Mooks, is more of a Type 1 with elements of Type 3 (the latter being openly encouraged in the Chorus). She is less sadistic than Nerat, being less willing to kill innocent people (just people, though). She also Jumped at the Call to join the Chorus, not being interested in the settled life she lived on her mother’s farm. In keeping with her Type 3 elements, she’s of the belief that the strong should lead, murdering their way to the top if necessary. If taken to fight the Voices, she claims that Nerat has grown weak and needs to be replaced.
Kills-in-Shadow is literally a Type 3. She is a bloodthirsty predator who willingly pledges herself to the player character, but only because she is convinced that the player character is powerful; she makes clear when joining that her loyalty is purely a matter of strength and she will readily turn on the player character if she is convinced they have grown weak. She is protective of younger packmates, though, be they fellow Beasts she looked after or fellow allies of the player character.
Bleden Mark is primarily a Type 4 with elements of Type 1. He has no interest in power or laws; he only serves Kyros because his attempt to kill him/her failed and Kyros offered mercy in exchange for service. He enjoys killing people, so as long as Kyros and Tunon give him fun targets to take out, he’s willing to continue serving them, though a sufficiently interesting player character can convince him to serve them instead.
League of Legends: Several champions are rampaging maniacs in various forms. Aatrox, Brand, and Cho'gath, as Omnicidal Maniacs, are probably the most "evil", while the most "chaotic" are Shaco, an Expy of The Joker, and Kled, a mushroom-addled lunatic who flies into a murderous rage whenever anyone other than himself or Skaarl is on "his property", a category that — according to Kled — includes pretty much every inch of Valoran.
Pathfinder: Kingmaker, having the Trope Maker's alignment system, has several canonical examples, some of whom are party members:
Tartuccio, a Guest-Star Party Member from the tutorial and later The Rival of your character for the first chapter. Tartuccio is a vain, backstabbing, manipulative and mean little bastard with no standards or morals and also a spy for Pitax. No matter which way the parties end up splitting Tartuccio quickly throws his other teammates under the bus for his own benefit.
Rengongar is a former slave from Numeria whose life was made a living hell by being a test subject for 'awakening' magic potential. Having been set free by the Player Character, Rengongar wants revenge on his former captors and to make sure he's never hurt again, and is willing to throw everyone else to the wolves to keep his own freedom. As long as he's not under direct threat, however, he's completely affable and friendly and has a Morality Pet in his life companion Octavia. Depending on how their personal quest ends up, Octavia can end up rubbing off on him and make him change alignment (it can also go the opposite way).
Nok-Nok is a goblin convinced he's The Chosen One of the God of Evil Lammasu, making him a goblin hero. Like most Pathfinder goblins (who are Neutral Evil) he combines a complete lack of impulse control with a Social Darwinist outlook and rampant pyromania, and adds to it an even more selfish streak and a love of stabbing things. Like Rengongar, he's perfectly nice to the Player Character as he sees you as a sidekick/mentor who will help him reach his destiny.
The majority of the game's Arc Villains are Chaotic Evil, like the Stag Lord, Tartuk and Hargulka, Armag, Irovetti, and the game's Big Bad Nyrissa as well.
The Demon ascension path is chaotic evil, and a Commander who embraces it gets a lot of alignment shifts in that direction and ultimately has to embrace it to continue the path to its apex. The majority of the game's demons and cultists, such as Deskari, Minagho, Nocticula and Bathomet are chaotic evil as well.
Camilla is a sociopathic Serial Killer hiding under a veneer of polite helpfulness. While clever enough to know how to survive by making themselves useful to greater powers, they are impulsive, murderous and can at best fake empathy and sympathy for others. They still despise and oppose the demons, however, because a society run by demons is too openly depraved for them to get their jollies.
Nurah is another secretly chaotic evil character. A former slave, the hypocrisy of watching 'good' realms and beings permit the system that abused and imprisoned them caused them to snap and pledge themselves to the demonic cause, seeing the open Might Makes Right system the demons practice to be more honest.
The Serpent Riders from the Heretic and Hexen games. While given little in game characterization, they are definitely evil and implied to be chaotic as the source of their power is called the Chaos sphere.
God of War III: Kratos, hands down, is the avatar of Chaos through this game, murdering civilians for sport on his way to achieving vengance against the gods and unleashing environmental disasters on the world as they die. As quoted in this trailer:
Zeus: In the end, he will suffer. In the end, we will triumph. In the end-
Kratos: There will be only chaos.
The Five Nights at Freddy's series has William Afton/The Purple Man. He killed roughly around 11 kids for seemingly no reason other than For the Evulz, and only becomes more eager to continue killing when he became Springtrap. The sixth game also implies that he deliberately set his own daughter to possess Circus Baby so she could become a murderer like himself.
Lawful Evil counterparts the Kzer-Za. The Kzer-Za believe that the key to their race's survival is to enslave everybody else, thus bringing order and hierarchy to the galaxy. The Kohr-Ah on the other hand believe that if there are no living sentient races, then they can never again be made slaves and kill. Anyone and everything that isn't them must die.
:Zeus: In the end, he will suffer. In the end, we will triumph. In the end-Kratos: There will be only chaos.