Le Chiffre in Casino Royale is a Smug Snake, albeit a very competent one. He's a mathematical genius who displays tremendous grace under pressure during poker games and is gifted at intimidating his opponents but pretty soon the cracks in his shell appear larger. When things start turning sour for him, he immediately starts to lose his cool. He's highly intelligent, but not quite so clever as he thinks himself to be. His entire plan throughout the film is just to pay off debts he got himself into with the world's terrorists by betting the wrong way with their money which shows his overconfidence and as Bond says "all he gets in return is a name he already has." He still wears a suit damn well though.
The criminal Waingro in Heat displays a smug expression whenever committing an low act like killing a guard during a heist for staring at him and enjoying a pie afterwards, murdering a underage prostitute or betraying his former colleagues to a common enemy.
The arms smuggler and film's protagonist Yuri in Lord of War is the epitome of the Smug Snake. An Honest John that refuses to confront the vehemence of his guilt and crimes by arguing that "I just sell guns, I don't pull the trigger". He taunts an honorable and idealistic weapons inspector, Valentin, by using the letter of the law to divert its spirit. Though by the end of the film he's still at it, he has everyone and everything he loves crumble around him. Interestingly, his character is essentially an amalgam of several real-life arms dealers.
The Chamberlain in The Dark Crystal infuriates his rivals with a simpering croon, like a mother trying to soothe a child. Though he's stripped of his rank and banished, his guile and persuasion are still impressive, and get downright creepy when he meets the Gelflings.
Vice-Counsel DuPont, the Big Bad in Equilibrium, who seems to be far, far too smug for someone who's supposedly emotionless (a clue that he isn't taking his Prozium, and earns himself a suitably anticlimactic Karmic Death for it.
Theron in Frank Miller's 300 (or the movie version thereof, at any rate). A wannabe political manipulator in a city-state full of warriors, Theron's manipulations succeed in delaying Sparta's march to war for a time, but he quickly gets his comeuppance when Queen Gorgo runs him through with a sword in front of the Council, which coincidentally exposes his Persian bribe money, thus exposing him as a traitor.
The movie Divorce, Italian Style has the Villain Protagonist Don Fefe (even the name is less than magnificent) who throughout the film plots to lure his ugly wife into adultery so that in keeping with traditional custom, he can kill her and her lover with impunity and marry his beautiful cousin. Outside of the loathsome nature of this plan, he is less than clever in carrying it out (finding himself in an odd position of being jealous of the wife he didn't give a damn for) and the movie ends ironically by implying that his new wife, the cousin, will be begin cuckolding him almost immediately.
Eddie Brock in Spider-Man 3 is, at least initially, a slimy, unctuous creep who sucks up to Jameson to advance his own career prospects, is a bit too creepy-stalkerish with Gwen Stacy, the 'girl he intends to marry' (although Gwen is quick to point out that they've only ever been out for a coffee once) and ends up manufacturing a photo of Spider-Man robbing a bank to frame the superhero and secure a staff job at the Bugle. Then Peter exposes his fake, he loses his job, and Gwen breaks up with him — and then he meets the Venom symbiote...
Any of the villains who aren't Hans (and maybe Simon) from the Die Hard movies. But since The Villain Makes the Plot, their presence doesn't deter from most fans' enjoyment of the films.
Fracture also shows a good contrast between a Smug Snake and a Magnificent Bastard, (or, considering how he screws everything upat the end, a much more high-functioning Smug Snake). The former is a smarmy prosecutor who believes he has gotten a completely open-and-shut case, and consequently has not bothered to do his job properly. The latter is a murderer who believes he has made himself untouchable despite the case against him seeming to be bulletproof, and is not worried about showing how confident he is. The reason you are almost rooting for the murderer is because his arrogance comes from having planned everything very carefully, rather than smugly assuming he's going to win. The fact that he's played by Anthony Hopkins certainly helps.
Paul Sarone from Anaconda. In addition to being a Manipulative Bastard, you could probably count the times that smug smile leaves his face on one hand. If you were missing a thumb.
Klytus from the 1980 Flash Gordon. Also Wicked Cultured, but with a strong dose of aristocratic snark. Occasionally loses his cool, but always has a bored, sneering dismissiveness for his opponents or a sleazy "with pleasure" for his boss—yet he badly overestimates how cowed Prince Barin is and gets thrown onto spikes for his trouble.
Louis Renault from Casablanca, although Louis is really just too cool to remain a bad guy through the whole picture, so he reforms at the end so he and Rick can fight Nazis together.
Both main mobsters in the The Dark Knight Saga (Falcone and Maroni). They're clever guys who've managed to keep a very nasty city under their control for a long time, but they're just not competing in the same league as the real supervillains in town... and yet, Falcone is clearly the most arrogant and condescending villain in Batman Begins, while Maroni is at least one of the most arrogant and condescending villains in The Dark Knight.
Bane: [Places his hand on Daggett's shoulder] Do you feel in charge?
Doctor Emma Temple of The Ring Two, a smirking, utterly insensitive psychiatrist. Samara uses a Jedi Mind Trick on Dr. Temple to make her commit suicide, which on the one hand is the least gory death in the series, but may be the most humiliating as it implies Temple is so Weak-Willed Samara can dominate her with a thought.
Colonel Zaysen from Rambo III. The Agony Booth recap gives an absolutely perfect distillation of this trope:
Zaysen will not go down in history as one of cinema's greatest villains, sad to say. He has all the tools: A decent sneer, a nasty sadistic streak, and a taste for chess to give him a cultured James Bond villain aura. But he never really becomes a character. Instead, the script has him simply go through the motions and expects that to be good enough.
The aptly-named Justin Hammer from Iron Man 2. While he is a massively rich military industrialist, and not above the odd bit of sceming, he comes off as an unbeliveable douche and a vaguely pathetic shadow of Tony Stark: his Hammer Tech weapons fail utterly, he can't cobble together an Iron Man suit knockoff to save his life, and it's pretty obvious that he's being played like a fiddle by Ivan Vanko. Even his trophy girfriend is one of Tony's cast-offs.
It's pretty telling that when it comes down to Hammer versus the crazy murderous Russian, the audience tends to root for the latter.
Tommy O'Shea, the Big Bad of Death Wish V The Face Of Death. A slimy, Irish mobster, he always manges to escape prosecution because he has a mole in the D.A's office but once Kersey gets his sights on him, he acts like its' a minor annoyance. Even when his dragon Chicki warns him not to underestimate Kersey, O'Shea is far too confident in his plans. Sadly, his overconfidence proved to be his undoing, as he wasn't savvy enough to realize he was a villain in a Death Wish movie and therefore, doomed.
Gríma Wormtongue as portrayed by Brad Dourif in The Lord of the Rings. He's slimy to the core, talks to everyone with an annoying sneer in his voice, and didn't prepare even nearly large enough a guard to ward off a small band of heroes who happen to be good fighters, and apparently not remembering to tell his guards why they needed to take Gandalf's staff. (The book, in contrast, makes clear that the doorwarden doesn't trust Gríma further than he could throw him — he lets Gandalf get away with bringing his staff because he believes that Gandalf means well for the Rohirrim, but that Gríma does not.)
Gaff in Blade Runner. Everything he says is some kind of sarcastic remark, and it's clear that he knows much more about Deckard's situation than he's letting on. Unusual in that he's technically on the side of the 'good' guys, though in a film that deals mostly in Gray and Gray Morality it's often hard to tell.
Lord Coward in Sherlock Holmes, who seems to spend most of the movie standing around looking rather smug with little reason to be. He does notably attempt to shoot Holmes when he gets the chance, but still fails miserably.
Jabba the Hutt in Episode VI: Return of the Jedi. Han offered money instead of his captivity and Jabba wouldn't listen; when Leia and Luke warned Jabba they could defeat him, Jabba and his minions didn't take them seriously at all. Even when being led to the Sarlacc Pit Luke said "this is your last chance; free us, or die." Jabba and his minions stil didn't take them seriously. Jabba had so many warnings, and so many chances for alternatives, that for him to still keep ignoring them made his Karmic Death all the more satisfying. In his defense (and who ever thought they'd hear that) he'd heard it all before. He'd had dozens, maybe hundreds of others in exactly the same place that the heroes were in, and clearly he had come off the better of it each time. In various EU works, he actually is more of a Magnificent Bastard than Smug Snake. But as far as the movies themselves go, no context is given for this dismissive approach. Also, "free us, or die" comes after Luke manages to defeat the Rancor; this should give Jabba some indication that Luke could be a potential threat. Even if he was a Magnificent Bastard before this, that doesn't rule out the possibility that he has turned into a Smug Snake since. (Even Palpatine, who was clearly a Magnificent Bastard in the prequel trilogy, showed signs of turning into a Smug Snake in Return of the Jedi.)
Admiral Motti's"this station is now the ultimate power in the universe" remark comes across as fairly arrogant in any context, but especially in light of what happened near the end of the movie.
Chad in In the Loop likes to think he's negotiating his way up the career ladder in the U.S State Department and effortlessly out-manoevreing those opposed to in. In reality, he a toadying little worm who is completely ignored by Linton Barwick, whose ass he tries desperately to kiss (Linton doesn't even remember his name), and is regarded by everyone else as a slimy little creep.
Inglourious Basterds has Major Hellstrom and, more unconventionally, a rare 'good guy' example in Bridget Von Hammersmark who is utterly disdainful of her allies but doesn't seem much (if at all) smarter.
Eli Sunday from There Will Be Blood is a charismatic religious fanatic who presides over a cult in the small American town where he resides. While his ambition is to be commended, he is nevertheless a hyptocritical bully whose faith in God crumbles when faced with adversity. When confronted with a bigger bully than himself in the form of raging Daniel Plainview, he is reduced to crying and screaming while begging for his life.
Shattered Glass presents Stephen Glass as one of these; he initially comes off as a humble, self-effacing and charming guy, but the longer he keeps it up and the longer we watch him we realize it's all just an act he uses to manipulate people, and the more we realize he's actually just a slimy, weaselly creep.
The douche-tacular Captain Styles of the USS Excelsior in Star Trek III. He exists for Kirk to tap-dance rings around.
Admiral Marcus from Star Trek Into Darkness counts as one. In his final scene, he goes on a rant on how Kirk started a war, "forcing" Marcus to step up to lead Earth in a time of impending war. The arrogance and Blatant Lies are enormous. Not only that, but he didn't take into account that Kirk has a habit of disobeying the rules, meaning he found out the details of his plan. Let's not also forget that he thought he could control a Badass like Khan...
The Other is also an example of this, as he's certain that Earth will surrender the instant his Chitauri launch their assault. He wisely becomes more cautious of the humans after the Avengers repel the invasion. This might qualify him as a subversion, as a key characteristic of a Smug Snake is an inability to learn from their mistakes, a weakness he clearly does not share.
In New Jack City, drug dealer Nino Brown's sliminess reaches its epitome near the end when he makes a deal with the prosecution for a reduced sentence. He gloats to the cop who tried to get him convicted and whose mother he killed years ago to come work for him when he's back on the streets, and praises the American justice system to the press. He is almost immediately publically killed vigilante-style by an old man whose life he destroyed earlier in the film.