Darth Vader himself, from the Star Wars franchise. According to George Lucas, the film franchise is fundamentally about Anakin and his progression from innocence to a force of good, his fall to evil, and subsequent redemption.
Louis Bloom in Nightcrawler is a sociopathic video journalist who has no problem with worsening local crimes happening around him for the sake of the camera.
Once Upon a Time in the West: Played completely straight in Frank. Although Jill is arguably the film's protagonist, a lot of it is told through Frank's P.O.V., and it is ultimately his actions that set off the main storyline.
Yuri Orlov in Lord of War is a gunrunner who sells weapons to anybody, including violent dictators and human rights violators. We're shown what a disaster his love life and family relationships are in such a way that you have to stop and feel sorry for him.
Truth or Consequences, N.M. is about a low-level mobster named Raymond Lembecke who, after being released from prison, decides to rob a big-time drug dealer with his girlfriend and partners-in-crime. The remainder of the movie shows Ray and his friends on the run after the robbery is badly botched.
Deathtrap: Michael Caine as a man who murders his wife and seduces his secretary.
Reservoir Dogs follows several thieves after a heist. Although one of them is actually a cop, they are all more or less equal in screen time.
Natural Born Killers, though the film muddies things by making the law enforcement officers creeps and murderers as well.
Big Jim Mc Lain features a "hero" who works for Senator Joseph McCarthy (yes, that McCarthy), and beats the living snot out of liberals in Hawaii. Made worse by the fact that this "hero" is played by John Wayne. To be fair he is targeting "communists", but the definition seems to be more than a little... general.
The Fiendish Plot of Dr. Fu Manchu, Peter Sellers' final film, is an Affectionate Parody (with roots in The Goon Show) that makes Fu Manchu charming and a bit sympathetic in his unrepentant wickedness. Having been thwarted so many times by the British, and on the brink of death, the whole plot hinges on him creating a youth elixir to save himself.
Nick Naylor of Thank You for Smoking is the "Sultan of Spin" and chief spokesperson for the tobacco industry. His Crowning Moment of Awesome comes when he testifies before a Congressional hearing that when his son, possibly the only other sympathetic character, turned eighteen and wanted a cigarette, he would buy him his first pack. The story softens his character considerably by making plain that he realizes the fact that many people see him as a villain, and good-naturedly takes this in stride.
Chuck Tatum (Kirk Douglas) in Ace in the Hole (1951). He's a washed-up, amusingly cynical, charismatic, and brilliantly manipulative newspaper writer who dooms a man to death in a collapsed cave by prolonging and milking the rescue attempt - he's confident the man will make it through several days in there - just so he can report on it and restore his career. He regrets what he does in the end, but it's doesn't much matter because it's a World Half Empty where most of the characters don't care about the life at stake, and instead take his lead and encouragement to profit off of the literal media carnival that springs up in its wake of this "Human-Interest Story".
The main character from Woody Allen's Match Point gets married to a rich woman mostly for her money while having an affair with his brother-in-law's girlfriend. Ultimately he gets the mistress pregnant, so to cover it up he kills her and her neighbor to make it look like a botched robbery.
Both the protagonists from Mr. & Mrs. Smith (2005), probably. Both were assassins, but there was really no clue as to just who their employers reported to or whether either organization was good or evil, or just what overall goals they had. (Jane did mention something to one target about "selling big guns to bad people" before she killed him, but there's no way of knowing if that was in any way typical of her hits.) Seeing as each of them seemed pretty decent to anyone who wasn't on his or her list, you might call them "Punch Clock Villain Protagonists".
Woody Allen loves the Trope, as Judah of Crimes & Misdemeanors follows a similar path to the protagonist of Match Point. Judah wrings his hands a lot, but he's still evil.
Henry, the eponymous character from Henry: Portrait of a Serial Killer Unlike other examples of this trope, though, he's not Affably Evil or an Anti-Villain in the slightest. In fact, he's so cold and emotionless that he comes across as barely human, and routinely commits some of the most horrific murders in film history.
In the Norwegian film Insomnia, the protagonist Engström begins as a moderately corrupt detective (though he's highly regarded by his peers). By the end, he's descended into pure evil, partially caused by the madness of working in 24-hour sunlight above the Arctic Circle but mostly due to his own inner lack of humanity. The final shot of his dead, haunted eyes is one of the creepier endings in film.
Kind Hearts and Coronets: The protagonist's mother, the daughter of a duke, is disowned by her family after eloping with an opera singer. In revenge, the protagonist plots to murder every relative standing between himself and the dukedom. While simultaneously leading on both Betty and Veronica. And it's all played for laughs.
Frank Abagnale Jr., the protagonist of Catch Me If You Can, is an adrift and young counterfeiter and con man who uses his natural cleverness to make some money, and his antagonist, Hanratty, is an FBI agent trying to, well, Catch Him if He Can. In the end Frank with Hanratty's support eventually goes straight.
The eponymous character of Charley Varrick is a career bank robber, who we first see robbing a bank. However, given that the movie is about him trying to escape the consequences when the bank he hits turns out to be a money laundry for the Mob, he played entirely fair with his fellow gang members until they tried to screw him over (at which point he unhesitatingly arranged for them to fall into the hands of the antagonists), avoided killing innocent bystanders (again unlike the antagonists), tragically lost his (fellow bank robber) wife in the opening scene, and faced off against a Mafia hitman, he's easy to root for.
Otis, which features a deranged serial killer who targets young women in order to relive his high school memories (or more accurately, his brother's). However, he apparently doesn't rape them.
The Australian psychological thriller Restraint has a female example in Teresa Palmer's character Dale, a stripper on a crime spree with her murderous boyfriend. She remains sympathetic due to a kind streak.
The "father/daughter" con-artist team of Paper Moon.
Tony Wendice in Alfred Hitchcock's Dial M for Murder and Steven Taylor in the pseudo-remake A Perfect Murder. Both discover that their wives (who are each independently wealthy) are cheating on them and, not wanting to divorce them and lose out on the money, cook up elaborate schemes to murder them instead.
The Usual Suspects revolves around a group of criminals, trying to get out from under the finger of the villain, Keyser Soze. It turns out that the protagonist, Verbal Kint, was the villain all along.
Jodie Foster's character from The Little Girl Who Lives Down the Lane. An interesting case, because her killing is more of a survival tactic than a true villainy, but her actions are a little too extreme to describe as "antihero". Plus, it's not (usually) so much a matter of physical survival, but of preserving what amounts to a set of hippie values. Which is subversive in all kinds of great ways.
Four Lions: a comedy about aspiring jihadist suicide bombers.
The eponymous main character of Mini's First Time is an utterly remorseless parricide. She is probably as close to soulless as a person could be, which is precisely what makes her so compelling to watch.
The protagonist of The Bad and the Beautiful is a ruthless movie producer who scruples not to lie, cheat, steal, seduce, and con to get his movies made. The film is narrated by three of the people whom he chewed up and spat out on his way to the top.
Bridget Gregory of The Last Seduction, a Con Artist who steals $700,000 from her equally crooked (but much less clever) husband and spends the rest of the movie scheming to bump him off and get away with it. She succeeds, and her Unwitting Pawn goes to prison in her place.
Tony Curtis's Sidney Falco of Sweet Smell of Success. He screws over and uses everyone he meets in the film, with the exception of his master, J.J. Hunsecker (as portrayed by Burt Lancaster).
Earl Brooks (Kevin Costner) of Mr. Brooks, a caring family man and philanthropist with a secret addiction to serial murder. Unlike a lot of examples, the good sides of his persona are real and not just a mask, making him highly sympathetic. Despite that, he's still a monster.
Matsu from the Female Prisoner Scorpion films is, not too surprisingly, a prisoner. Put away for attempted murder, she goes on to kill and cause to be killed many more times before the series ends, her victims including the prison warden at least two detectives and several other policemen. The facts that one of the detectives, the man she tried and failed to kill, seduced her and arranged her rape purely to allow him to arrest the rapists and corruptly take over their business, that the prison warden tortured her, locked her underground in chains for a year, had her raped and ultimately tried to stage her death, and that she never kills senselessly, only makes her less villainous relatively speaking.
The trio of the protagonists in Fassbinder's Film NoirLove Is Colder Than Death. The first of them is a pimp and rapist, the second is a violent killer-for-hire working for Mob, and seemingly the least evil of them is a prostitute, but she also doesn't disdain of murdering people, including Innocent Bystanders.
Maindrian Pace in Gone in Sixty Seconds (1974) steals cars for a living, though he makes sure that the cars are insured. The remake averts the trope. Although the protagonist is also a car thief, he's being blackmailed into performing the heist by the real villains.
A Clockwork Orange. The first act of the film has Alex DeLarge, our protagonist, as a blatant villain. In the rest of the film, however, he's a helpless victim. In the film version of the story, the biggest villain turns out to be the government, who try to play God with a man's mind, screw up, and ultimately sweep it under the rug and make a deal with a psychopath.
The protagonist of I Stand Alone is a violent ex-butcher who pummels his pregnant girlfriend into a miscarriage, plans to murder random people who cross him, and molests his daughter.
Sue Shiomi as Yumi Higaki from Sonny Chiba's Dragon Princess is a killing machine with violent revenge the one thing on her agenda. She also fits into the Type III Anti-Villain category and gets a Bittersweet Ending in that while she suffers the same fate as her father in avenging the loss of his arm, she survives and is able to live a more normal life.
The title character from Caligula, which depicts the reign of the Ax-Crazy Roman emperor.
O-Dog in Menace II Society. Unlike some other examples of villains protagonists, he is not sympathic or nice, has no redeeming qualities, and has very few traits of Affably Evil. Rather he is a sadistic Ax-Crazy who does not hesitate to kill.
Ryunosuke in The Sword of Doom is an amoral samurai who's cruelty earns him the hatred of almost everyone around him.
Neil McCauley (played by Robert De Niro) in Heat is a ruthless bank robber, but he has an equal role in the story as Vincent Hanna (played by Al Pacino), the cop trying to catch him.
Lou Ford in The Killer Inside Me is an accomplished serial killer and domestic abuser masquerading as an honest cop, and genuinely enjoys all the murders he commits.
All the protagonists and antagonists in the Spanish movie Acción Mutante are villains, fighting each other for selfish reasons like money, sex or spite - not even because the other villain's kind of evil is worse. Even the minor characters are unsympathetic (e.g. the misogynist hillbilly miners; the ridiculously-posh, biased TV journalists).
Chad from In the Company of Men is a rude sexist Jerkass who gets a woman to fall in love with him just so he can break her heart later on for his own amusement. He runs a business and treats his employees like dirt. He later betrays his "friend" Howard, getting him demoted at work and driving him and his girlfriend to depression.
While her quirkiness does make her endearing at certain points, Mavis Gary from Young Adult spends most of the film doing everything she can to break up a happy, wholesome marriage (with a newborn girl, no less). Not to mention she is absolutely horrible and demeaning to most people who are unfortunate enough to come across her.
Terrence McDonaugh in The Bad Lieutenant: Port of Call New Orleans. He's a Rabid Cop who also a drug and gambling addict, steals from other cops and suspects, tortures people he interrogates, and blackmails female suspects to have sex with him. The only redeeming qualities he has is that he still loves his family and girlfriend, and draws the line at point blank murder. By the time the film's ending comes around, he still hasn't changed his drug-inducing habits one little bit and goes largely unpunished for all his crimes.
Paul from The Manhattan Project, when he's not bullying the school nerd with chemical explosives, he's building nuclear weapons that he then uses to hold the military hostage until he gets his way.
The Firefly Family are the villains of House of 1000 Corpses, but the sequel, The Devil's Rejects, makes them the protagonists of the movie. They're utterly depraved and valueless serial killers, but the audience is able to relate to their deep emotional ties as a family. To spice things up, the movie has a particularly crazy Knight Templar hero who is himself quite compelling.
Daniel from Pain and Gain. The interesting thing is the survivors and family accused the filmmakers of portraying Lugo and his co-horts as "antiheroes who just made a few mistakes," which is about as far as the trailers got. In reality the film doesn't make them out to be good people in the least, and instead shows that they are stupid, selfish people who torture and kill others for their money (Paul is an exception, who is a devout Christian dragged into this scheme, also being a combination of two other characters).
Alonzo the Armless is the central character in The Unknown. He is a murderous and obsessive knife-thrower who leaves a trail of bodies in his wake and has his arms amputated in an attempt to possess the woman he loves.
Cactus Jack Slade in the Western parody The Villain, though he's a thoroughly inept and bungling one.
Cabin by the Lake centers around horror movie writer Stanley Cauldwell, who's knowingly and obviously evil as a depraved serial killer of women.
The protagonists of The Eagle Has Landed are a group of German commandos trying to assassinate Winston Churchill under orders from Heinrich Himmler. The film does establish that the commandos themselves are honorable men concerned only with their mission and are disgusted by the war crimes they witness, even if their bosses might be mass murderers.
Every character in Conspiracy (which features an Ensemble Cast) is a high-ranking official of a totalitarian regime engaging in wars of conquest and extermination, while their objective is to organize a continental genocide.
William "D-FENS" Foster from Falling Down. He's dangerously insane and becomes increasingly violent, but at the same time he's also clearly a victim of powers beyond his control, and the audience is encouraged to feel catharsis through his actions even as the movie condemns them.
American Me: The main character Montoya Santana is a leading member of the Mexican Mafia.
Archie Channing from Quigley started out as a JerkassCorrupt Corporate Executive who was rather unforgiving to his employees, but after a car crash gets him sent to Heaven, he comes back to Earth in the form of a Pomeranian in order to make up for all of the selfish things that he did, which is what incites his Heel–Face Turn as the movie goes on.
Te Wheke, the rebel leader protagonist of Utu wants to kill every white person in New Zealand. These include the women and children, and any Maori who won't join his rebellion.
Bill Wiliamson of Rampage is a trigger happy lunatic who goes on a killing spree, shooting up his home town and killing many people before skipping town with stolen money to start another rampage. In the sequel, he takes a studio hostage and later blows it up and kills everyone, before giving a little girl a gun and telling her to go home and kill her parents and herself. He claims he kills to strave off overpopulation and fight against the corrupt government, but his aditude toward his victims reveals this to be a shallow excuse.
In Kiss of the Tarantula, Susan is a spider-obsessed Creepy Child (who grows into a creepy teen) with a Sympathetic P.O.V.: her first victim is her mother, who was plotting her father's murder. The next set were teens who broke into her house, threatened to rape her and killed one of her pet spiders. (and it's implied she was just trying to scare them). Bo, on the other hand, she killed to shut him up.
Telly, the main character in the independent film Kids, is everything you don't want your child to be.
Downfall is a film which follows Adolf Hitler as he lives out his last days in World War II. You hardly get more bad guy protagonist than that. The film flits between depicting him as sort of a dignified old captain going down with his sinking ship, and depicting him as an irrational, condescending and spiteful man who believes sympathy is a weakness and has no problem with blaming others for his own failures and demanding the German people fight to the death down to the last man, woman and child in horrid conditions while he sits in a comfortable bunker without firing a single shot at the enemy.
From Dusk Till Dawn: Seth Gecko and his deranged brother Richie are a pair of bank robbers on the run from the law who kidnap a preacher and his sons in order to get to Mexico. They end up in a strip bar infested with vampires, fighting to survive. Well, Seth does. Richie is the first to die.
In Purgatory, it looks like Blackjack and his gang of outlaws are going to be the protagonists of the movie, and the early scenes focus on them exclusively. However, this turns out to be a Decoy Protagonist once they arrive in Refuge.
A Bucket of Blood follows Walter Paisley, a young man so desperate to befriend the local beatniks that he kills people and makes sculptures from the bodies.
The Halloween remakes by Rob Zombie put Michael Myers as either the main protagonist (in the first half of the first movie), or dual protagonist alongside Laurie. The remakes go into depth to make Michael more sympathetic, giving him a rough upbringing rather than him being a normal boy who just decided to kill his family, and even made some of his kills either self-defense or mercy killings. Laurie is also more villainous, dreaming about killing her friend Annie in the sequel, and having violent outbursts. The movie ends with her trying to kill Dr. Loomis, before the police shoot her down.
The Last Supper is about a group of progressive liberals who start killing people whose politics they find evil. Whatever morality they might have began with gets slowly discarded as they descend a slippery slope of murder.