Ace High has Cacopulos, who is likable and easygoing despite being a cunning and dangerous criminal. He's pretty much a slightly smarter, more mellow Tuco.
Max Lozoya from Don't Turn the Other Cheek is a likable scoundrel who goes along with being mistaken for a revolutionary hero so he can get to treasure easily.
Agora: There's hardly any completely maleficent villain; the Christians are, after all, still human, and while they were very fanatical and Knight Templar-ish, they still helped the poor and each other. In fact, the only person who was truly villainous was the Bishop, Cyril of Alexandria, who himself is very Affably Evil, caring for his people and all.
American Gangster: Frank Lucas is a very polite, well-dressed man who cares deeply for his family and takes his mother to church every Sunday. Despite this, he is frequently shown to have no qualms about gunning down people who get in his way in cold blood, or blighting Harlem with heroin for pure profit.
The A-Team: Lynch is just so adorable about being evil.
Lynch: We do have laws, they're just cooler than yours.
Austin Powers: Dr. Evil, much like the villains from 'James Bond', invites Austin into his lair, makes him a meal and designs tailor-made futuristic clothes for him and his love interest to wear. Taken to an even higher level in the third movie where, in the final act, they team up to take on the secondary antagonist of the film.
Avatar: Most viewers saw Col. Quaritch in as this, probably against James Cameron's intentions. The guy will do everything in his power to keep the people under his charge alive and safe (and his men obviously adore him for that), and he seems to be a fairly nice -if strict- person to have around... as long as you are not a Na'vi or a human who likes the Na'vi. It's telling that he actually got Jake a ticket home and a new set of legs for his efforts.
The Babysitter: Max may look like your stereotypical jock, but when a bully is egging Cole's house he halts his attempted murder to give him advice on how to stand up for himself.
Babysitter Wanted: The villain chats merrily with the Final Girl as he's carving up the body of another girl. His accomplice later gets mad at him for being so friendly.
Badlands: Kit speaks politely to just about everyone, right up until he shoots them. After he gets caught, he is polite and cooperative to the cops.
Batman and Robin: Despite being considered the worst Batman film, one of the few redeeming qualities is that its version of Mr. Freeze is a fairly three-dimensional villain. His crimes are committed only so he can fund his research into finding a cure for his terminally-ill wife, as opposed to being violent for the sake of violence like the last handful of antagonists. He comes close to a Heel–Face Turn at the end by helping Batman cure the dying Alfred. He does get some occasional Kick the Dog moments, such as executing a henchman for walking into his office when he wanted some privacy.
Bedazzled: Elizabeth Hurley as Satan in the 2000 remake. She's out for Elliot's soul, but she generally acts friendly and sympathetic to him most of the time. Even after he nullifies their contract and saves himself, she stays polite and cordial before seeing him off. Actually a subversion, since the end of the film reveals that she's not evil at all.
Cash On Demand: Colonel Hepburn from the Hammer Horror film is a friendly and amiable man. When he visits a bank, he is more friendly to the employees, and knows more about them personally, than the bank manager does. The reason he's visiting the bank is to rob it.
City of God: Benny is one-half of the crime duo who systematically murdered their way to controlling all the organized crime in the City of God favela. However, he's also a friendly party-boy who reins in the Ax-Crazy tendencies of his partner.
Pinball introduces himself as a "Armed robber, arsonist, dope fiend, and a hell of a nice guy who just got caught", which you'd think would land him in Faux Affably Evil territory, but being played by Dave Chappelle does wonders for a con.
Swamp Thing is such a jolly, good-humored sort that you almost forget that he's an integral part in a scheme to bust out a planeload of mass murderers, terrorists, and gangsters. He's a drug smuggler himself, but even his actor defends him, pointing out that he didn't kill anyone or get in their faces...
Garland Greene, a cannibal who committed murders that "made the Manson Family look like the Partridge Family", has to be rolled onto the plane in full Hannibal Lector vestements, and even has the other murderers and psychos scared of him, spends the entire film sitting peacefully, chatting with others, having a tea party with a little girl, and singing "He's Got The Whole World In His Hands."
Conspiracy: This HBO movie is an extremely chilling example of this trope. A group of intelligent, cultivated, soft-spoken men having a secret conference in Germany in 1942 about what to do with the "storage problem" of the Jews in Europe. And it is based on the minutes of the actual meeting.
Crimson Peak: Sir Thomas Sharpe is friendly to everyone he meets, and unwaveringly loyal to everyone he loves. Unfortunately, the only person he has ever loved is Lucille, and he helps his older sister lure three women to their deaths before he begins to fall in love someone outside of his abusive, incestuous relationship with her and starts to realize that what he's doing is wrong. It's unclear how much he understood their actions were wrong before that, given the nature of his upbringing.
Demolition Man: Dr. Raymond Cocteau is a kindly old man running the police state of San Angeles and directs its inhabitants' lives completely for what he believes is their own good. Lampshaded by Simon Phoenix, who compares the man to an "evil Mr. Rogers".
Dial M for Murder is a classic thriller featuring Tony Wendiss, a man who concocts The Perfect Crime; blackmailing someone to kill his unfaithful wife while Tony is across town, thereby securing both his alibi for her death and the money she's left him in her will. Wendiss never loses his charming, upper-class, English politeness, even when he is caught by his wife, her boyfriend, and a Scotland Yard inspector at the end of the movie.
Simon Gruber from Die Hard with a Vengeance. Like his brother, he is polite and courteous. Even when robbing the Federal Reserve, he only kills guards who try to fight back. Those who don't resist merely get tranquilized with heavy sedatives. Hell, he even honors his fallen henchmen as he and his crew escape with their ill-gotten gold. At the end, it turns out he never was going to blow up any school. Even he thought Hans was an asshole, but that didn't stop him from wanting revenge on McClane. This behavior is evident in his underlings, who actually avoid killing Zeus when they could have, and even take a bomb from him, thinking "a kid could find it."
District 9: At least initially, Wikus in several ways; he's an amiable, well-liked low-level functionary...who is casually racist and brutal towards the oppressed aliens, and laughs and makes jokes when 'aborting' alien eggs.
Dracula (1931): "Good Evening. Welcome to my humble abode. My, how beautiful you are. I hope you will stay the night. Oh, where are my manners? Allow me to introduce myself. I am Count Dracula."
Drunken Master 2: John, one of the main antagonists, is some form of this. He's very cheerful for almost the entire film, except when being brow-beaten by the British Ambassador he's working for, and when Fei-Hong is beating the crap out of him at the end of the film. He even gives a cheery thumbs-up and a big grin after kicking Fei-Hong onto burning coals.
Juan from Duck, You Sucker! is initially set up as a mean, ruthless, and amoral bandit, then we get to know him and find out that he's just an ordinary guy trying to look out for his family in a world where stealing is the only way to survive.
Enemy at the Gates: Major Koenig qualifies as this for much of the movie. Sure, he's out to kill his sniper counterpart, but he's polite about it, and when one character, a young boy acting as an informant, hears of his rival's supposed death and is trying not to cry, he tells him that it's understandable since he was one of the boy's countrymen. When he figures out that the kid's been informing on him to the Russians, instead of confronting him, he hands him a chocolate and gives the kid a Mercy Lead, telling him not to come back. The kid comes back, so Koenig hangs him from a telephone pole to use as bait to lure out the Russian sniper.
Gangs of New York: Bill The Butcher is polite, has a moral code, a deep sense of honor...but he just hates those bloody Irishmen invading American soil, and God help you if you get into a knife fight with him. To the point where Amsterdam is conflicted because he finds himself liking the man he intends to take revenge on for killing his father. He does have a few Kick the Dog moments where you realize the guy is not merely a Memetic Badass but pretty reprehensible, so the audience is conflicted too.
As in the novel on which the film is based, Don Vito Corleone is warmhearted, reasonable, prefers to think of his partners as "friends", and happy to perform the odd favour for his less-than-fortunate neighbors. True, he does inform them that they might have to do a little quid pro quo, but contrary to Amerigo Bonasera's worries, all he usually asks for is a free service from their business. He even adopted Tom Hagen and eventually allowed him to become his personal advisor - even though he knew that none of the other Mafia bosses would approve. Vito's still in charge of one of the most powerful Mafia families in America, and he's not above the occasional murder or extortion to back up the usual income from gambling and union racketeering. However, Even Evil Has Standards, which Vito demonstrates in his refusal to deal in drugs and prostitution (the most contemptuous line in the film is when he says, "Tattaglia's a pimp"). And, to his credit, he does his best to keep his children and his civilian friends as far away from crime as possible.
Having learned from his father, it's unsurprising that when Michael takes over the business, he also fits this trope; however, though well-mannered and gracious, he lacks Vito's degree of warmth - which, combined with his ruthlessness, eventually begins to distance him from his friends and family.
Tommy DeVito. Despite being an Ax-CrazyPsycho for Hire, he acts like this to his comrades and his mother, showing a lot of respect to them. It helps that, for all his faults, Tommy genuinely cares about his friends ("I didn't want to get blood on your floor") and is emphatically loyal to them in a life where loyalty and covering for each other is everything.
Jimmy can be very civil and is a caring father. Towards the end, Henry and Karen perceive the Faux Affably Evil vibes from Jimmy, who is up to no good with the Hills by then.
Henry: Your murderers come with smiles. They come as your friends. People who cared for you all your life.
The Great Escape: Colonel von Luger, the commandant of the POW camp is certainly more affable than the Big Good, being a Luftwaffe soldier who sees his enemies as Worthy Opponents and is only obeying his superior's commands out of duty rather than ideology. He's always polite towards his prisoners and was adamently opposed to the execution of the recaptured escapees. This was Truth in Television.
The Green Hornet: Benjamin Chudnofsky. He has a politeness and an inferiority complex that's pretty disarming, and he tries too hard to seem intimidating in the end, but is dangerous when people point out that he isn't 'scary'. This character is played by Christoph Waltz, the same actor who portrayed Hans Landa. Waltz rather excels at playing Affably Evil characters.
Gremlins 2: The New Batch: The Brain Gremlin is an erudite, genetically-altered gremlin who merely wants what everyone wants, and what you tropers have: Civilization! The Geneva Convention, chamber music, Susan Sontag...
Throughout all three films of The Hangover, Leslie Chow only wants to be friends with The Wolfpack.
Home Alone: Harry and Marv are very friendly towards Kevin despite their menacing attempts to kill him, most notably in the first film where they almost hit him with their van and warned him to watch out next time.
The Iceman: Richard Kuklinski (Michael Shannon) is a good husband a loving father and a ruthless contract killer with a rumored tally of over 100 kills. Even creepier: the film is based on a true story.
The Imaginarium of Doctor Parnassus: The plot of the movie is set in motion when Mr. Nick (Tom Waits), having already won the soul of the Parnassus's daughter in a wager made decades before she was born, agrees to allow Parnassus to try to win it back on the eve of its forfeiture (even though Parnassus has absolutely nothing to offer to sweeten the pot). Throughout the course of the story, it becomes clear that Nick is deliberately trying to lose this wager to avoid ruining his Friendly Enemy status with Parnassus, to the point that he tries to physically restrain the daughter from deliberately damning herself to Hell just to spite her father and, when that fails and he wins the bet, he immediately offers Parnassus a new wager so he can try to win her back again. This leads to one of the film's best lines: "Damn. I won."
Into the Storm (2009): Josef Stalin is shown as this. While he is a tyranic despot, one can't deny the man has manners. Lampshaded by Churchill's butler, Sawyers:
Sawyers: "I drink to marshal Stalin, a much nicer man I thought he'd be."
Inglourious Basterds: Colonel Hans Lands is unfailingly polite, while being a Nazi officer who takes obvious pride in his work
I, Robot: VIKI and the NS-5's are polite and calm while trying to take over the world.
(The normally loyal robot blocks Susan's way) Robot: Please remain calm. Robot: Please refrain from going to your windows or doors. Susan: Deactivate! Susan: Commence emergency shutdown! Robot: We are attempting to avoid human losses during this transition.
And later, before attempting to kill people
Robot: You have been deemed hazardous. Will you comply?
The books take this to a whole new level with characters like Marc-Ange Draco. Apparently, you can be guilty of drug-running, extortion, and murder, and effectively be a good guy as long as you're really, really nice and charismatic in personality.
Never Say Never Again is an independently-produced remake of Thunderball featuring Klaus Maria Brandauer as an utterly charming version of Maximilian Largo. Shame about the psychosis lurking just under the easy-going, good-humoured facade...
Kill Bill: Bill is very friendly and likable, as well as a loving father, despite being a self-proclaimed "murdering bastard," and helps the Bride reach an epiphany about herself at the end of the duology. He also genuinely cares for, and loves, The Bride. He's only trying to kill her because she broke his heart.
Killshot: Mickey Rourke's character Blackbird is a Professional Killer. When he's not on duty he's a somewhat easy fellow to get along with. Even when he has a reason to kill he's fairly conservative and is typically courteous to his victims.
The King of Comedy: While the film's premise centers around him premeditatedly committing a major felony against an innocent person, Rupert Pupkin is nonetheless a mild-mannered, sympathetic underdog. He displays several traits in pursuit of his dream - persistence, levelheadedness, and an aptitude for thinking outside the box - that would be considered admirable in countless other contexts. Contrary to audience expectations, he never experiences any sort of meltdown during the film and never tries to actually hurt anyone. After he and his girlfriend watch his monologue on Jerry Langford's show, he even considerately switches the television back to the movie that the other bar patron was watching!
Kingsman: The Secret Service: Valentine is a down-to-earth, genial fellow who's mildly Adorkable, doesn't care at all about his billions and is primarily concerned with saving the world so much that he's willing to kill most of humanity to do it. He shows a dislike of politicians who "stand for nothing but re-election", he's genuinely charming, makes friends easily and absolutely believes he is doing the right thing. It's little wonder so many of his co-conspirators come over to his side willingly. He even mourns the death of his previous kidnap victim, Dr. Arnold. He's also appalled when he shoots Harry in the head, as this was actually the first time he had ever killed someone, and he's Afraid of Blood.
The Lady Vanishes: Dr. Hartz is quite a nice guy, which is shocking to modern audiences considering he turns out to be an assassin, and a Nazi at that. (The film was made in 1938, before the world was aware of the Nazis' atrocities.)
Lock, Stock & Two Smoking Barrels: Big Chris is a hitman, but is overall a nice guy, and a good dad to his son, Little Chris. But so much as lay a finger on Little Chris, and the affable part goes out the window.
Andre Baptiste, a brutal African warlord, is friendly and welcoming to Yuri. Andre Junior, who is a renowned cannibal, is even worse but no less affable, if only around Yuri.
Yuri himself, who is the protagonist but is frankly an amoral (at best) arms dealer.
The Lost Boys: David is a murderous vampire and all-round delinquent, yet he's very friendly and fun-loving. Most of his victims tend to be whoever goes out of their way to piss him off.
As well as his father, Max (Edward Herrman).
Lucky Number Slevin: Both villains were Affably Evil, but The Rabbi especially. He even, ultimately, seems to genuinely believe the main character's assurances that he is not the person they think he is, and sympathizes with his plight.
Man Bites Dog: The main character Ben is a Serial Killer who kills randomly, but he really is nice to his friends, inviting them to the restaurant and offering to help cover the costs of the movie.
In Captain America: Civil War, Zemo is very a noble and wise human being who shows great respect towards the Avengers despite his vendetta against them for creating Ultron who killed his family. He is also very understanding of other people and would show great sympathy towards them, as he did with T'Challa whose father he killed and framed Bucky for the murder.
Thanos of all people turns out to be this as well. Unlike in the comics, Thanos is actually a Well-Intentioned Extremist who thinks the only way to save the universe and its limited resources is to wipe out half the life in the universe. He commends bravery and sympathizes with his opponents, and is a a man of his word.
Masterminds: Mr. Bentley (played by Patrick Stewart), the villain of , is charming, polite, levelheaded, and witty. He also equips his men with Instant Sedation dart guns during the initial takeover of the school and orders them not to injure anyone while repelling the cops' attempts to retake it (although it's really only through the magic of Hollywood ballistics that no one is killed).
The Minus Man: Vann Siegert is a serial killer, but he uses a painless poison to kill his victims. He seems to genuinely sympathize with the Durwins, tries to reciprocate Ferrin's feelings for him (although this ends poorly for both of them), and seems extremely disturbed by Jane's apparent murder at the hands of Doug.
Motel Hell: The brother and sister duo, Vincent and Ida, are a hospitable couple who run a nice little motel and provide some great meat pastries which are made out of people.
Muppet Treasure Island: Long John Silver seems to genuinely care for Jim even as he's threatening to strangle him, and has a boatload of charisma (although being played by Tim Curry may be a factor here).
Night of the Demon: Julian Karswell is charming, charismatic, pleasant, loves his mother, hosts parties for local children...and is a Satan-worshiping cult leader who uses black magic to kill casual acquaintances.
Notorious: The villain is about the nicest, most debonair Nazi you'll ever meet.
Once Upon a Time in the West: Cheyenne is a cheerful, friendly fellow who seems perpetually amused by the events in which he is caught up. He's also a confessed murderer and bandit leader. It helps that A) he's not the villain of the film, just the local badman whose territory the villain trespasses on, and B) all of his crimes take place off-screen (just outside the door in the case of his slaughter of his prison escort).
The President's Analyst: Dr. Schaefer ends up abducted by The Phone Company. Arlington Hewes, its president, is unfailingly pleasant and polite while he explains to Dr. Schaefer why he needs his professional knowledge for his world-domination plan — and while he inflicts high-tech torture on Schaefer when he refuses to help.
Psycho: Norman Bates may be a psychotic murderer, but he's also rather personable and endearing when the "mother" side of his personality isn't in control.
Pulp Fiction: Jules Winnfield is actually a pretty nice guy, for a mob hitman. Just don't say "What?" to his questions. In fact, all of the gangsters in the film are affable and friendly, even when they're casually waving a gun in your general direction.
Reefer Madness: Sure, Jack Perry is perfectly willing to give marijuana to teens, but he's probably the most charming drug dealer ever.
Red Rock West: To some extent, Lyle From Dallas. Protagonist Michael Williams first meets Lyle after nearly being run over by him - Lyle is very apologetic about it, makes sure he's okay, gives him a ride back to town, bonds with him over their shared past with the Marine Corps, and buys him a drink. Since this is the first we see him, his turning out to be the bad guy would almost be a twist, were it not for him getting very angry about Michael initially refusing his offer to buy him a drink, as well as the fact that he's played by Dennis Hopper.
Return to Oz: The Nome King displays a disturbing mix of affability and subtle condescension towards Dorothy and her friends (his counterpart in the books, though, was more of a cackling Card-Carrying Villain). The film Return to Oz plays the same "all a dream" card that the film of The Wizard of Oz played, and the Nome King, in this case, is supposed to be a direct analogue to the psychiatrist running the asylum where Dorothy is being treated at the beginning of the film. He himself is quite Affably Evil in his own right, warmheartedly declaring that electroshock therapy is "just the thing to cheer Dorothy up", words that the Nome King repeats later in the film.
Rustlers' Rhapsody: The villains realize that the hero, Tom Berenger, always beats "bad guys," so they hire a "good guy" to fight him. The "good guy" appears to be an even nicer person than Berenger and gains the upper hand, but Berenger soon learns that he's actually a lawyer, and is then able to defeat him.
Saboteur: All the villains in this Alfred Hitchcock movie. In between planning and executing acts of sabotage against military installations, we see a kindly grand-father playing with his grand-child, a rich socialite who hosts a charity-dinner, a father who ponders whether he should let his son have long hair, a man who gives their hostage a milkshake, and a man who frets that the confrontation with the hero will make him unable to go to the philharmonica with his niece later that evening.
Saw: John Kramer of the films is fairly approachable, polite, and truthful to the victims whom he tests and places in life-threatening, yet, escapable traps. Unlike his apprentices, John appears to genuinely want his victims to pass their tests and survive his traps. He is also honest at all times.
Tony Montana of Scarface (1983) is quite friendly and sociable in the first half, for a murderous drugpin. The second half not so much, after getting addicted to his own supply. His best friend Manny more so.
The Operative: There is no shame in this. This is a good death, for a man who has done fine works.
Sherlock Holmes (2009): Dredger is an extremely large thug who will wreck the place and crush you (with his bare hands, if necessary) if that's what he's been paid to do... but he's surprisingly personable about it.
Shutter Island: Subverted, where we are led to believe that Dr. Cawley is like this. As it turns out, his genuine personality is just affable, and, in fact, he has been running a very elaborate simulation in order to snap Teddy Daniels (real name: Andrew Laeddis) out of his self-induced fantasy that he is a federal marshal, in order to make him come to terms with his wife's death.
The Silence of the Lambs: The cannibalistic Dr. Hannibal Lecter is an interesting example in that nobody can be really sure if his affability is just an act, particularly as he's prone to sniping insults at visitors who displease him. The simple answer is that he is genuinely nice and respectful to people who are genuinely nice and respectful to him, exhibiting this both towards Clarice Starling and an orderly who broke his arm to stop him from attacking a nurse, but was otherwise always respectful and never rude. As the orderly points out at one point, Lecter "prefers to eat the rude".
Sleepaway Camp: Angela Baker practically becomes some kind of murderous Genki Girl in the second and third films. She also really likes the "Happy Camper" song, and often honestly doesn't seem to understand why her victims are scared of her.
The Stepfather: The eponymous Serial Killer from this series of films is fond of stuff like dogs, model building, and gardening; he's actually a pretty nice guy, at least, until things stop going his way. There's a scene in the second movie where he sits down to breakfast and only starts eating after his Rice Krispies pop; he looks as giddy as a kid when they make their trademark noise.
Suicide Kings: Charlie Barrett is about the nicest guy who ever fed anyone to their own dogs.
Lex Luthor is played like this in the original Superman films, especially by Gene Hackman; at least, he can be a smooth talker and affords Superman respect as a Worthy Opponent. Yet he's willing to sink California to the bottom of the sea for profit.
Man of Steel: Big Bad General Zod maintains a calm and cool presence, and firmly believes himself and the other Kryptonians to be one step above human. However, unlike the theatricalZod before him, this version of Zod cares about his troops, speaks to both Clark and Jor-El (including Jor-El's "ghost") as if he knew both his entire life (in the latter's case he does), and generally wants to re-create Krypton (even if that means destroying Earth to do so). He still does, however, commit violent acts like invading Metropolis and also threatening Mrs. Kent in-order to find Clark, whom he wants not only to join him but obtain his blood to birth to a new race of Kryptonians.
The Third Man: Harry Lime is incredibly likable and charismatic, as well as being an amoral war profiteer and murderer.
21 Jump Street: Eric may be badass drug dealer, but he is actually a very nice guy.
22 Jump Street: The Yank twins are rather friendly considering their envolvement with the drugs.
Two Hands: Pando is plenty affable, but utterly intolerant of anyone who tries to cross him.
Unbreakable: Elijah Price is well spoken, expensively dressed...and is actually a Super Villain, or at least a mass murderer. So affable, in fact, that until the very last scene, you would never guess that he was the villain all along, making this the last truly shocking M. Night Shyamalan twist.
The Untouchables: Robert De Niro as Al Capone is a Magnificent Bastard who goes from pontificating on the joys of baseball one second to savagely murdering an associate with a bat the next. Every word that passes his lips is met by sycophantic laughter.
Viago, one of the main vampire flatmates is a vampire who routinely murders people for their blood. He is also a sweet, easygoing guy who tries to be friends with everyone he can and has the philosophy that if he's going to eat someone he'll at least give them a very nice night first.
Petyr might be a millenia-old vampire who Looks Like Orlok, but all the other flatmates speak highly of him and he seems to listen to Nick when the latter asks him not to feed on Nick's friend Stu.
The Wicker Man (1973): Lord Summerisle and the rest of the islanders. Sure, they'll lie and deceive people into being used as human sacrifices. But they'll do it all while singing and dancing and dressing in silly costumes.
In X-Men: Days of Future Past, Bolivar Trask is polite, believes in world peace, and does not even hate mutants. However, he still allows often fatal experiments on mutants to achieve this end.
In François Truffaut's Shoot the Pianist with Charles Aznavour, the two gangsters who were betrayed by the titular pianist's brothers are easygoing fellows who have nice Seinfeldian Conversations with anyone they kidnap, and even react somewhat politely when their hostages escape.