The Avengers: Ultron is of the Intelligent Monster variety. This Killer Robot started out as a methodical criminal mastermind and Master of Disguise willing to cooperate with human supervillains in order to defeat the Avengers, but a few reincarnations later, he went full Robotic Psychopath and Misanthrope Supreme, reflecting the darker aspects of his creator Henry Pym without any moral and rational restrictions and most of his plans boil down to petty vengeance against Pym and the Avengers while causing plenty of death and destruction in the process, with little care for his original goal of becoming the ruler of a robotic utopia, sometimes on a galactic scale as seen in Annihilation: Conquest,.
Batman: It depends on the writer, but The Joker is almost quintessentially Chaotic Evil, insane and indiscriminately destructive, enough as to why he's pictured in this trope's page. He puts the emphasis on Chaotic — he may not be as likely to jump off a bridge as cross it, but he's almost as likely to blow it up. The only indication we get that he has any restraint at all is in the storyline where he has terminal cancer, and we find out what he's like when he has even less to lose. Sometimes the Joker is too chaotic to be evil. One story has him driving a truck through the wall of a television stage to hijack a quiz show; as soon as a woman gets a question wrong, he grabs her and pulls her towards his button flower, and she screams for mercy — but instead of acid, he sprays her with ginger ale. He goes on like this for the rest of the strip, punishing incorrect answers with normal, run of the mill pranks, and generally acting like his Silver Age counterpart. All the while, the station manager refuses to cut the transmission, as a live Joker rampage would boost their ratings sky high; he gets increasingly frustrated waiting for the Joker to stop playing around and get to the carnage, but he doesn't. Eventually Batman arrives to stop him and Joker surrenders peacefully, not having harmed a single person for the entire strip, but before he leaves, he reveals he was filming the station's control room the entire time, and starts playing the footage; then he looks at the camera and says "So, who's the real sicko, America? Me, for carrying out this little prank? The producers and executives at the network, who let it all happen — or is it you people, who mindlessly watched it all on your television sets?". The last panel is the producer holding his head in his hands while the Joker laughs insanely. Most fans agree that when the Joker does the Harmless Villain routine, it's always because, in that particular situation, it's much more psychologically and emotionally scarring. Letting everyone know that you enjoy a harmless prank and coldblooded murder in equal measure does wonders for your sinister reputation. He would probably be a type 2 (more evil than chaotic) as he likes hurting and killing people so much.
Captain America: The Red Skull, is an example of intelligent Chaotic Evil. While he originally started as Lawful Evil, he eventually moved here. Not content to seize control of a country from within, he and his close friends in HYDRA actively seek to cause mayhem and destruction, undermining the governments of the world in both subtle and openly vicious ways. He's so nasty that even most of the other Big Bads of the Marvel Universe dislike him.
Daredevil: Psycho for Hire Bullseye loves killing, pure and simple, both for the challenge of a difficult kill and the sheer thrill of committing them. He gets paid a fortune, as he is one of the world's premier Professional Killers, but he barely spends any of it, and his oft-repeated comment is that he has more money than even resident evil billionaire Norman Osborn. He would be Neutral Evil if not for the sheer rate that he killed people — he can barely go a Story Arc without leaving a whole pile of corpses, regardless of whether he was paid to kill them or not, and he generally kills on whims with little to no regard about the bodies being found or him being caught (not that the average cop would survive trying to catch him anyway).
D.R. & Quinch: The titular characters are this to the core, albeit mostly for laughs (theirs and ours). They prank the Phi Delta frat house by nuking it, and indirectly engineer the destruction of Earth to get back at their dean for suspending them.
Empowered: Willy Pete is a sociopathic fire-elemental with a more-or-less human mind that lives to indulge human appetites such as food and sex in the least socially acceptable manner possible.
Evil Ernie: The titular Evil Ernie, who spreads death and destruction so he can get Lady Death's love and and because he hates order, peace and heroes.
Fables: Mr. Dark and Max, The Pied Piper. Mr. Dark is the embodiment of fear of the unknown, and enjoys spreading death and misery to this end. Max is a psychopath who thinks the world owes him whatever he wants, and flies into murderous rages when his demands aren't instantly met. He also has a penchant for luring entire cities of children to their deaths.
Bloody Mary makes it clear that the only reason she works for the crooked man is because it gives her more opportunities to kill and spread suffering. She is a sadistic sociopath who admits to becoming aroused by her own cruelty.
Justice League of America: Prometheus, Grant Morrison's penultimate 'Anti-Batman', definitely fits into this trope. He's got Batman's eye for discerning weakness but none of his restraint — in his first appearance, he very nearly murdered the entire Justice League. In a later comic storyline, he caused the deaths of thousands upon thousands of people just to prove he could best the heroes of the world (because said heroes had gotten rather serious after Final Crisis and Batman's apparent death). He did all this while strapped to a chair in League headquarters, calmly mocking the League as their every attempt to out-think him failed, until they finally were forced to release him to get the codes to shut down his machines (a destroyed city, maimed hero, lost loved one and at least a hundred thousand dead later). Anti-Batman indeed. Unfortunately for Prometheus, this made things beyond personal for Green Arrow, who proceeded to Pay Evil unto Evil.
Lobo: Lobo fits this perfectly; all the stuff he does is mostly because he felt like doing it. He wiped out his own race as a school project, for which he gave himself an A.
Loki: Ghost Kid Loki]] uses this exact phrase to describe the original Loki: "His alignment is totally Chaotic Evil!"
Nemesis the Warlock: Nemesis himself fits here by his own admission. Whereas Torquemada is the incarnation of Lawful Evil as the psychopathic god-dictator of the hostile human empire of Termight, Nemesis himself is a bloodthirsty demonic alien who loves his arch-enemy for posing an amusing threat. At first he seems like Chaotic Good until he reveals his true motivations, lambasting the person who thought that Torquemada being evil must have meant that Nemesis is good. As he explains, the forces of Khaos and Order can be either.
Sin City: The Yellow Bastard says it himself: "I get to do whatever I want!" It definitely doesn't help things that he's protected from any punishment he might otherwise receive for his horrible acts by his corrupt U.S. Senator father.
Sonic the Comic: Although he went through a period of amnesia, Fleetway's version of Super Sonic is otherwise a hardcore Type 4. While he starts out by wiping out whatever evil he's up against, he is ready to murder his friends and spin-dash the entire planet if he doesn't burn himself out in time. In fact the only reason he kills is for something to do, since being completely invincible in every way is boring, and Super Sonic gets bored faster than a sack of live weasels. It doubles as Fleetway's explanation as to why Sonic doesn't go Super more often.
Cletus Kasady, a sadistic serial killer bonded to the Carnage symbiote who sees violence, bloodshed, and mayhem as the ultimate freedom.
When fully corrupted, the Venom symbiote is little better than its progeny, seeing itself as an agent of chaos and seeking only to vent its rage and satiate its ravenous appetite. Eddie Brock in his first voyage as Venom also befits this alignment: causing as much havoc as he needs to and even severely injuring and killing those who stand in his way, just to completely dismantle Spider-Man - his at-the-time arch-nemesis - and his life as both civilian and hero.
The Green Goblin could serve as an interesting example. Norman Osborn himself is Neutral Evil, working within and without the system as the situation demands in a ruthless quest for money and power, as well as petty vengeance on Spidey. But Osborn is also mentally unstable and genuinely insane, and sometimes (and originally) his Goblin identity was a case of Split Personality. His Goblin side also originally wanted the same things — maybe even for Osborn — but is clearly much more homicidal and reckless. In recent issues Osborn has given up his Goblin identity to be a straighter Villain with Good Publicity under the name of the Iron Patriot (and towards Lawful Evil), but he is unable to properly control his homicidal tendencies to the point where it seriously threatens his plans, which is being exploited by his evil rivals.
Thanos: Thanos the Mad Titan is also high-functioning Chaotic Evil — methodical, calculating, but ultimately usually driven by whatever he feels like doing at a given time, or a nigh-omnicidal romantic obsession with Death, and usually a Straw Nihilist who doesn't believe any moral or ethical authority, answers to nobody but himself, and is The Unfettered in everything he pursues.
Transmetropolitan: President Gary 'The Smiler' Callahan. The entire reason he became president is so that he could fuck everyone over. He says so himself!
Sabretooth. He absolutely loves killing and thinks of himself as a hunter stalking a kill. However, he's incredibly self-centered and views everyone who isn't a potential victim as someone to use to further his own goals, and he's exceptionally good at manipulating people into doing exactly what he wants them to do without them even knowing it. Absolutely no one ever trusts him with anything, and that's because he has a very long list of people whom he has either murdered or completely screwed over once they've served their purpose. What separates him from your standard aimless moron is that he's very, very deliberate about it and knows exactly how to get away with what he does; like Bullseye, he WOULD be Neutral Evil if it wasn't for the incredible body count that he has to his name. He's a Type 4 through and through: he lives for nothing but violence, bloodshed, and (if it involves Wolverine) psychological torture, but he's terrifyingly cunning and crafty and will always find a way to rope large amounts of people into his latest scheme without their even knowing it.
Spiral is practically the Joker of the Marvel Universe in that she's unpredictable, and the impression is clearly given that without Mojo there to hold her leash, we'd all be in serious trouble.
Lawful Evil, he eventually moved here. Not content to seize control of a country from within, he and his close friends in HYDRA actively seek to cause mayhem and destruction, undermining the governments of the world in both subtle and openly vicious ways. He's so nasty that even most of the other Big Bads of the Marvel Universe dislike him.