The Monarch's henchmen, particularly #21 and #24, are losers and social outcasts who are just trying not to get killed. In one episode, #24 is overheard to complain that working for the Monarch was the only job he could get after the factory he worked at closed ("It was either this or the Army"). In another scene, they both try to recruit new henchmen by searching for out-of-work deadbeats in need of a paycheck. They accidentally hire a bunch of hardcore gangsters they can't control.
Over the course of the show, it's revealed that both heroes and villains are really just bored idle rich people who use their wealth to live a fantasy lifestyle. The Guild of Calamitous Intent keeps the battles from getting out of hand with a laundry list of rules and regulations. Arch-nemeses are gained by an interview process rather than personal vendetta. Battles are sometimes even scheduled like play-dates. Anyone who doesn't play by the rules is rounded up by the Guild, and anyone who is legitimately dangerous is taken out by the secret group Sphinx.
The punch-clock nature of "arching" is especially emphasized when Sgt. Hatred becomes the new arch-enemy of Dr. Venture. He intentionally treats Venture gently and politely, just to annoy The Monarch, who holds a true vendetta against Venture but is not allowed to arch him. There is also Red Death, a villain of horrific legend among the Guild. Although his reputation is completely deserved, Red Death is shown to be a reasonable and loving family man (albeit one with a red Skull for a Head) because he has learned to "separate his work from his life".
The inversion to the rule might be Monstroso, whose day job as head of a corrupt and powerful law firm actually makes him more evil than his arching after hours.
Ron, from Kim Possible, once stumbled into a bunch of Dr. Drakken's goons in what appeared to be an employee's lounge, suggesting that they're all punching a clock somewhere too. (At one point, Drakken mentions he holds an employee picnic for them.) In a further parody, one of the episodes features a trip to Henchco, a temp agency that does nothing but supply henchmen (and equipment) to aspiring villains.
At some point, all Kim Possible villains have had some version of a punch-clock villain. One went so far as to involve Kim and Ron in a fight between punch-clock villains and punch-clock spies.
Even Shego clocks off for the weekend if they're still in the planning stages of the Evil Plan.
Or at the end of the (inevitably failed) plan, unless Drakken drags her to Karaoke Night (where the civilians politely clap as Drakken sings; yet another example of an off-duty villain).
Fortunately, while Drakken's an incompetent villain, he's a pretty decent boss to work for; when Shego took a Christmas vacation in "A Very Possible Christmas", she was surprised to learn that Drakken had footed the bill for her vacation, including hotel accommodations and meals.
When Drakken gets a cold that's going around, his temporary partner-in-crime actually hires someone from a temp agency. The guy gets into his job, seeing new career opportunities around every corner.
Shego calls in sick, and while she's off the clock, she stands there watching as Ron hauls away the MacGuffin.
Homer unwittingly ends up working as a Punch Clock Villain for megalomaniacal but very affable CEO Hank Scorpio in The Simpsons. When Hank mentions he's "having problems with the government" (actually a full-scale base invasion straight out of James Bond), Homer expresses sympathy, but doesn't join in the fight (though he earlier prevented the escape of "Mr. Bont").
Wooden from The Scarecrow only works with Count Grisham because he pays him lots of money. Sure enough, when Grisham decides he's going to kill Polly, he immediately races off to warn her.
The Shocker started out like this in The Spectacular Spider-Man. He was a Hired Gun, who seemed fairly honorable. After his initial defeat, his grudge against Spider-Man seemed rooted in his wanting to do the job he was paid to do.
Also, Sandman, who maintains his lack of a villainous nature from the comics. He's only in it for a "big score", not all the vindictive vendettas most of the other villains have (he often says how much he hates revenge), and generally tries not to hurt anyone (except Spiderman and the cops) when on a job. This becomes even more clear in a recent episode, where he, while waiting for a contact, helps a kid get rid of some bullies, and, after accidentally setting an oil tanker on fire in a fight with Spiderman, helps save the crew, and almost kills himself containing the explosion.
Many Fire Nation soldiers are portrayed this way in Avatar: The Last Airbender. Although there are some that seem to enjoy being cruel, most are just normal people doing their jobs.
As well as Ty Lee and Mai, who are only doing evil due to being intimidated into it by Azula (Ty Lee) or being bored and needing something to fill time (Mai.) Mai takes it further than Ty Lee, on more than one occasion refusing to fight if she doesn't feel it worth her time, regardless of what Azula might do to her.
Certain episodes show that the Fire Nation Soldiers, by and large, don't even view themselves as Villains. The Fire Nation uses very liberal amounts of propaganda on the populace, and many are convinced that the war they're waging on the "lesser nations" is in their best interests.
In one of the final episodes, Sokka manages to take over a ship from the Fire Nation Airship fleet, by dumping the soldiers into the sea. During a conversation between 3 soldiers, they are portrayed as decent people...who were on their way to burn an entire country.
When Unalaq takes over the Southern Water Tribe by means of his own army and an army of Dark Spirits, a member of the Northern Water Tribe says that he should have instead stayed at home with his mother-in-law if he wanted to be surrounded by evil.
Korra and Asami are captured by the Earth Queen's forces. When Korra and Asami's attempt to commandeer the airship causes them to crash into the desert, the soldiers help them build a sandsailer and their captain declares Korra's beef with the Earth Queen "above his pay grade" and lets her go. (Not that he could take on the Avatar, but he proved to be grateful.)
The two Earth Empire soldiers that capture Ikki in the Season 4 episode "The Calling"; they strike up a rather civil discussion, bonding with Ikki over snacks and how they feel left out of big, important events (Ikki's middle child syndrome and the soldiers being forced to guard a small outpost while the rest of the army marches on Zaofu). Eventually, they even help her find Korra's hiding spot, and she leaves them a few rolls after Jinora and Meelo think she's their captive and knock the guards out
In Metalocalypse, Dethklok's manager, Charles Foster Ofdensen, is quiet and restrainedly affable, but will kill or torture anyone threatening his "bread and butter". Given that Dethklok are unambiguously a force for evil in the world (though a popular one and only one of a few), and he also doesn't care how many people are killed or maimed by Dethklok as long as there will be no untoward consequences for the band and his job, I think he qualifies as a villain.
Every antagonist (Revengeancers not withstanding) on the show falls into this category, one way or another; Even the Tribunal is only out to get the band because they challenge the status quo and it's their job to maintain it.
Lemongrab of Adventure Time is a tyrannical ruler who sends everyone to the dungeon for a million years. When he doesn't have a considerable position of power, however, he's just your average, mentally unstable, run-of-the-mill jerk who's only a threat to himself. He only acquired that position of power because it was his duty, not because he wanted to. And we all saw how eager he was to be there...
Mixmaster and Scrapper in Transformers Animated worked for Megatron because he had the better oil, and because he didn't try to scare them off. They really had no vested interest in Megatron's cause, and were only really motivated to fight when Starscream shot their oil. With their construction worker theme, it wouldn't be surprising if they used an actual punch clock.
Furthermore, they started out as friends to Bulkhead, one of the Earth team Autobots, and in "Human Error, Part 2", Scrapper joined up with Sari's group of Substitute Autobots to break Soundwave's brainwashing of the "first-string" Autobots.
Several Looney Tunes shorts where Ralph Wolf is trying to steal sheep away from Sam Sheepdog. There is an actual punchclock in this one, and both the wolf and dog punch in and out at sunrise and sunset. They also get an hour long lunch break, during which they eat lunch together and occasionally have a smoke (probably the reason why television doesn't show these anymore).
One specific instance that highlighted the punch-clock job aspect of it was at the end of one episode, Sam actually told Ralph that he has been working too hard and to take tomorrow off (it's implied this is because most if not all Ralph's injuries in the episode where self-inflicted via disasterous accidents - akin to Wile E. Coyote's mishaps with Acme Products -, unlike the usual injuries at the paws of Sam.)
Taz replaced Ralph when Sam resumed his role in a Taz-Mania episode.
Jack Spicer begins to cross into this territory during the second season premiere of Xiaolin Showdown, after a temporary alliance with the heroes comes to an end. When Omi pleads with him to not return to evil, Jack sighs and says that, though he's still going to fight them for control of the Shen Gong Wu, he promises they'll go out for ice cream sometimes when they're all off the clock, which cheers Omi up.
Walter Shreeve in Batman Beyond started out like this: he tried to kill Bruce Wayne, but only because he was pressure into it by his boss Derek Powers, after Powers threatened to fire Shreeve from his respectable (but nonprofitable) career of sound engineering research. However, he was then caught wearing his super suit at his workplace, meaning that he would unable to go back without being arrested, prompting him to embrace the moniker Shriek. Then, a battle with Batman caused him to go deaf, so he embraced full-on, city-threatening supervillainy to get his revenge.
Dr. Doofenshmirtz's evil plans are a routine; he usually won't even start trying to use his newest invention until his arch-nemesis (and best friend) Perry the Platypus shows up to foil him, and he seems to realize that he usually loses. He also has a teenaged daughter who lives with him part of the time; she fits this trope too, though far less enthusiastically, as if assisting her father were simply a normal chore. His plans usually involve creating potentially evil devices for silly, petty reasons.
Suzy is only mean to Candace whenever her brother's around (since she threatens her control over him), and is nice when she's "off the clock."
Buford refers to himself as a bully, but spends free time with his usual "victims" if there's no major bullying to be done.
The Justice League episode "Flash and Substance" has Captain Cold moaning about how crime isn't paying enough for him to make his mortgage payments.
The Mukhtar from Aladdin: The Series, an assassin who specializes in hunting down and killing genies. Not because he has anything against them personally (although that may have been the case in the past). Nowadays, he does it because that's simply what Mukhtar do; it's the only purpose for him. He's actually The Last of His Kind, and is now Only in It for the Money. In his second appearance, makes a full Heel–Face Turn after Genie saves him from a Man-Eating Plant.
Strike breaking lowlife Scab on Minoriteam is really just trying to feed his kids with villainy. And the Black Coq works for the White Shadow because he has nowhere else to go after losing his family and restaurant.
General Molotov is pretty friendly whenever he's off-duty. This is especially notable since he works for Lucius.
Samy isn't really a villain, but since he works for Lucius he counts as this.
A sketch on Robot Chicken featured Jason Voorhees eagerly awaiting Friday the 13th, where he went on his normal killing spree. The following day, he is disappointed to go back to a normal routine.
The Robot Chicken Star Wars sketches have Gary the Stormtrooper, a Mauve Shirt who stars in a few sketches. He's happily married, loves his daughter, and although one of the ones who killed Luke's aunt and uncle, it was actually an accident.
An episode of Cow and Chicken had Chicken trying to confront a bully on the weekends. The bully says he only bullies on the weekdays and spends the weekends helping the poor.
From Gargoyles, Pack member Dingo is pretty clearly just there for the paycheck, and gets increasingly disgusted with his teammates as they slip further into Psycho for Hire-ness. Ultimately, he decides he's had enough and has a flat-out Heel–Face Turn.
In one episode of Sealab 2021, Sparks reveals himself to be a madman bent on world domination, and offers Marco a position in his organization. Marco considers the job, depending on the benefits package.
Hinted at in a G.I. Joe episode, when the heroes search a COBRA office and one of them, reading some documents, remarks "Hey, they've got a dental plan!"
Later played straight in a profile book, where it's revealed that the vast majority of Cobra's blueshirt grunts were perfectly ordinary people who simply wanted a better life.
In South Park, Satan is portrayed in this fashion. He is also rather meek, insecure and Affably Evil, certainly less evil than Cartman, and chats pleasantly and enthusiastically with his victims (who appear to only be truly bad people) after torturing them.
Played for Drama in "Fatbeard" where Cartman and some South Park students go to Somalia to become pirates. One of the pirates explains to Ike and Butters that he would prefer going to school instead of attacking ships, but robs ships because otherwise he would have no money to support his family. He lives everyday fearing death when attacking a ship, or not getting anything to help his family. This causes a My God, What Have I Done? moment in the two, when they realize a pirate's life is full of hardship.
Ramon: Then why are you working for Castro? You know his stance on homosexuality!
Charles: Because, commie, I have something called a "mortgage."
The villain of "Movie Star" also counts. She even briefly considers not carrying out her duty as a sleeper agent until she remembers that the Soviets said she'd get to direct...
Total Drama could apply to many of the antagonists throughout seasons, who see their actions as purely strategic moves, and it is hinted that they aren't nearly as vicious outside of a competitive setting.
Heather: I was only playing the game the best way I knew how. It was never personal.
This is especially notable in the case of Alejandro, who shows zero remorse for any of his actions, as long as it gets him further in the game. However, in the end, he has nothing against any of the contestants, and once he and Heather are both eliminated in All-Stars, their relationship becomes as genuine as any other on the show. While it appears that when there's money in it, both still act villainous, but outside of the game, it is clear that Alejandro is generally a nice person when he has no reason not to be.
Young Justice has a strange example in Lobo's cameo: he arrived on Earth searching for his mark, beated up the guards, Batgirl and Wondergirl because they were in the way, showed Batgirl and Wondergirl that the guy they were protecting actually was an alien spy, and then left with his mark and no ill feelings.
Space Jam features the Moron Mountain workers who get supercharged by stealing some NBA All-Star players' skills with a magical basketball, turning them from the shrimpy Nerdlucks into the hulking Monstars. Despite maintaining a fanatical devotion to their stogie-chomping boss, however, this trope gets subverted in the end:
The "World Famous" Flim Flam brothers, who try to drive the Apple Family out of business so they can secure the local cider market, are only technically bad guys because they're taking aim at the Apple Family. All their claims about the quality and quantity of their cider and how superior it is to the Apple Family's are 100% spot on, and the only reason they even get the opportunity to take down the Apples to begin with is because Granny Smith accepts a challenge from them with nothing whatsoever to gain from it. It's not until their second appearance where they're actively conning ponies with good old-fashioned snake oil and emotionally blackmailing Applejack into endorsing it that they cross the threshold into true dick country.
The FixedIdeas from Cyber Six are this by virtue of simply being too darned stupid to be anything else. When left to their own devices without an order to follow, they pretty much just chill out with one another or try to coax out a stray cat (Which was actually Data 7 tricking them) so they can pet it.
In the animated version of The Return of the King the Orcs are implied to be this in contrast to their usual portrayal as Always Chaotic Evil. While marching they sing that they don't want to go to war but Sauron and their Officers tell them to. This may be close to Tolkien's idea that many of the soldiers fighting for evil are actually misguided and serving their masters due to fear and lies.
Dastardly and Muttley in Their Flying Machines: The Vulture Squadron consists of incompetent and moronic grunts who just do what they are told and only the promise of a medal or a furlough can give them any desire to seriously try to catch that pigeon.
Muttley, Dick Dastardly's canine co-hort on Wacky Races, has been described as villainous but has been known to bite the hand that feeds him.
Killara and his band of mercenaries in Kulipari: An Army of Frogs. Killara himself starts to take a liking to the hero Darel and lets him off on technicalities of his contract ultimately leading him to taking a larger payment from Darel to betray Marmoo.
Killara: There's only one rule for mercenaries: We don't fight for a cause, we don't fight for glory, we fight for money.
Star vs. the Forces of Evil: Buff Frog starts out a loyal lieutenant to Ludo who rules a castle's worth of monsters. By Season 2, he's a single father struggling with feeding a dozen adopted children with odd jobs that he no longer has the evil to properly pull off. He's got no other options since the monsters are quite poor compared to their Mewni neighbors.
Peridot from Steven Universe is definitely one of these, as her job was to re-establish the homework warp pad, manually re-activate the Kindergarten's underground lab, and report progress on the prototype clusters as well as the full size one. She doesn't care for the Earth because it's just a job. Once she's done, she'd leave and the Earth would be destroyed. However, upon being captured, she is eventually convinced to help build a drill to stop the cluster (mainly because she's going to be stuck there when the cluster goes off), and eventually is convinced of Earth's beauty and value. She then preforms a Heel–Face Turn on Yellow Diamond and calls her a clod once she realizes that she won't change her mind about destroying the Earth, becoming a crystal gem.