Weyoun of Star Trek: Deep Space Nine gets a few of these moments. There's one where he is analyzing (or trying to analyze) a painting, and asks Major Kira (a good guy who is under an occupation force that is under his command) what she thinks of it...genuinely, with no sinister undertones whatsoever. There's also a clip from the final montage of the fabulous episode "In The Cards" showing Weyoun thoroughly enjoying the crack-pot "Cellular Regeneration And Entertainment Chamber".
The first time he visits the station, he spends some time playing dabo in Quark's. An extremely bored Dukat asks why he's playing such a ridiculous game, to which Weyoun replies "I like games!"
Also ordering various meals through the food replicator. He explains that while his taste buds were shaped by the dominion leaders to perceive only one specific taste (a native type of nut from their homeworld) in order to keep them humble, he loved experiencing various types of textures and crunchiness in alien cuisine.
Invoked in "Defiant" when Gul Dukat laments to Sisko he'd rather be doing this. Before he got called to deal with the Maquis stealing the Defiant to attack Cardassian ships, he was about to head back home so he could go to his son's eleventh birthday party.
When the big bad of season 7 of 24 escapes to his house because his first plan fell apart around him, what's the first thing he has to do? Make excuses as to why he has no time for his girlfriend. How does he get to his house after his plan is foiled? Public transportation. What does he do once he gets there? Starts to make himself a sandwich. Meanwhile, the real Big Bad, Hodges, is shown to be watching the day's events and is already having a sandwich, with his sidekick encouraging him to relax.
Glory, near-unstoppable hell goddess, got regular cuts to her bathing or trying on new dresses. She is even shown buying supplies for an evil ritual from the Magic Box. Since only Buffy, who wasn't there at the time, knew what she looked like, the Scoobies were completely oblivious to the fact that they had just met the Beast. Cue major Oh, Crap! reactions from them when they realize just what they sold Glory and who she is.
MayorWilkins would always find time to attend to his public duties and look after himself while trying to become a giant demonic snake. The Mayor's checklist demonstrates this. After one ritual, we see that his list says, "Call Temp agency", check. "Become Invincible", check. Next item: "Meet with PTA". We also have scenes of him playing miniature golf, discussing about his favorite comics or treating Faith like gold.
In "A New Man", Giles and Spike run into each other while Spike is 'house hunting' - visiting crypts with a tape measure. Spike has also been seen walking home with groceries, playing 20 questions with his girlfriend, and hanging out in bars.
Or on Angel, after Darla comes back to life and Drusilla turns her back to a vampire (it's complicated), one of the things they do is clothes shopping. It does involve doing horrific things to the sales clerks, but still...
Wilson Fisk is introduced browsing in an art gallery, where he meets Vanessa. He later takes her out on a date, which is interrupted by Anatoly trying to barge in to speak with him. It ends badly for Anatoly.
Fisk's second date with Vanessa goes a bit more smoothly due to him buying out the restaurant, the bombing of Hell's Kitchen notwithstanding.
Cottonmouth's henchmen can sometimes be found throwing dice in the park on their lunch break.
Luke Cage: Damn. You guys actually take lunch breaks like real employees, huh?
Mariah puts up with being part of Cottonmouth's meetings with fellow criminals at Harlem's Paradise because she likes the musical guests he manages to headline.
Willis "Diamondback" Stryker is a fan of the Delfonics. When Shades tries to give him an update while he's watching the band perform at the club, Diamondback shuts him down saying "Shh! I like this song."
At one point, Turk is seen playing chess with Bobby Fish.
In "The Sound of Drums", the Master is shown enjoying Teletubbies while simultaneously planning mass genocide. This is a Call-Back to a 1970s episode where the Master watches an episode of The Clangers while simultaneously...
One of the novels has the Third Doctor grimly wonder what evil scheme the Master might be up to now...cut to the Master patiently waiting for his order in a Chinese takeaway.
"Frontier in Space" : the Master has just captured the Doctor and Jo, strapped them into his prison ship, and started flying towards his base of operations. He trades some evil banter with the Doctor, sits down at the consoles and...picks up a book and starts reading. Hey, even diabolical masterplans have boring bits in them.
Sylar eats frozen yogurt as he stalks Peter, Claire, and Ted from afar.
The entire first season, we kept hearing about this shadowy, diabolical mastermind called Daniel Linderman. What's he doing when we finally see him? Making chicken pot pies. He even gives a little speech about how to make one.
When not murdering, kidnapping, or generally terrorizing the Survivors, the Others enjoy book clubs, barbecues, and friendly games of football and ping pong in their hidden, well-guarded commune.
The members of a terrorist cell Sayid infiltrates spend their time playing Half-Life.
Supernatural did this with new Big Bad Lilith in the Season 3 finale, No Rest For The Wicked. It's hours until Dean's Deal with the Devil comes due and he goes to Hell. To prevent this, the brothers are planning to go after Lilith. At which point, we cut to Lilith...having a birthday party. Admittedly, this birthday party involved terrorizing and murdering the family of the little girl she'd possessed (this is Supernatural, after all), but it was still a birthday party.
Interestingly averted with a later villain, Crowley. While much more Affably Evil than Lilith or even Lucifer, when he becomes the Big Bad of Season 6, he's only ever shown torturing monsters or making deals with Castiel.
However, in Season 8, he takes a phone call while standing in a field, surrounded by adorable goats.
Played bizarrely with Death. The first time Dean meets him, he's sitting in a pizzeria casually enjoying a pizza pie, which he invites Dean to share with him. He's also killed the entire staff and all of the other customers for seemingly no reason except that they were there. When Dean asks him not to destroy Chicago, he nonchalantly agrees because he likes the pizza.
The Wire is about the lives of both cops and drug pushers, so there's an awful lot of this in every episode. Some notable examples include:
In season 1, Jimmy McNulty is able to make a major break in the Barksdale case from the complete chance event of spotting underboss Stringer Bell while both are doing their shopping. It also causes McNulty to get in trouble with his ex-wife due to having his kids tail Stringer, and accidentally losing track of them.
A particularly metaphorical scene in the first episode features several hoppers taking a break to play checkers with a chess set. D'Angelo tries to teach them the rules to chess, drawing parallels to the drug trade to help them out.
A funny scene in season 3 happens where Herc and Carver bump into Poot and Bodie at the cinema when they're all out with girlfriends.
Similarly, the squad only learns what adult Avon looks like because they observe him coaching a cross-town basketball game.
When stick-up man Omar Little runs out of Honey Nut Cheerios, he walks through the most dangerous streets in Baltimore in his bathrobe to buy some more. As he passes by, drug dealers toss him their stashes and run for their lives.
Even Marlo Stanfield, the closest example of a pure evil character, is shown picking up chicks in bars and planning a celebratory trip to Atlantic City.
Most of the drug kingpins in the city are periodically shown hanging out at legitimate businesses they own. For Prop Joe, this includes a pawn shop where he repairs electronic appliances, presumably just because he enjoys it.
During the early seasons of Miami Vice, it was common to see the week's given drug dealer/pimp/gun-runner etc, doing the most diabolical things, like...hanging out on the beach, dancing at the club, and trying on leather pants in some trendy Miami shop. Well, not leather, because leather and the Miami heat don't mix, but you get the point.
The reimagined Battlestar Galactica does this with the entire Cylon race. Throughout Seasons 1 and 2, the viewers get clues that the Cylons are planning something with the nuked Colonies, having left several cities intact and brought heavy machinery to clean up the mess, but otherwise showing no clues as to what they are doing. Given the Mind Screwy nature of the show, the audience isn't sure what to expect. Then, towards the end of Season 2, we get a Cylon point-of-view episode where we learn that Cylons are repairing the infrastructure, spending time in coffee shops, working in gardens, sitting and chatting around parks, and generally doing the stuff done by the humans they displaced. Including killing each other every now and then.
New Caprica and Season 3 onwards also treat us with glimpses of life aboard the Baseships. Apparently, when not committing genocide and shooting civilian ships, Cylons spend their time living in their personal Happy Place, doing Thai-Chi naked, listening to the ramblings of Hybrids, repeatedly committing suicide to get a glimpse of things not meant to be known, and bickering with each other on every decision.
UK Sketch ComedyBig Train loves this trope. One recurring sketch has what is essentially Ming The Merciless doing his daily chores, such as cleaning the house, checking his mail, and angrily yelling out the answers to questions of a quiz show he's watching on TV. Another sketch has Wolfman and Dracula hanging out in a public toilet (apparently at a conference of some sort), bad mouthing the other monsters. Which results in an Awkward Silence when The Mummy walks in.
The mutants from Vintergatan liked to get out and get backrubs — perhaps a bit more villainous considering they forced one of the heroes to do it, but still. Also, The Count from the newest installment, At The End Of The Milky Way, is, from time to time, seen playing with small figurines, complete with making silly voices for them.
Standard fare on every incarnation of CSI and Law & Order. When the criminal is apprehended, they will, the majority of the time, be in the middle of something incredible mundane. Justified in that most 'bad guys', in this case, are not career criminals, and have generally committed crimes of passion or opportunity, rather than opting for the life of a supervillain, but see it enough times and you'll become very wary of the fellow ahead of you in line for ice cream.
One of the people behind Criminal Minds stated that the aim in the episode "The Big Wheel" was to showcase a day in the life of a serial killer. This was definitely a non-humorous use, as it only emphasised the tragic situation the UnSub was in. A few other episodes have done it as well.
Due to having a Serial-Killer Killer protagonist, much of Dexter features him eating breakfast, going to work, eating lunch with his sister, and spending time with his girlfriend and the kids. We see the Ice Truck Killer do his day job and spend time with his girlfriend. And Dexter actually goes shopping with Miguel Prado, though that was for knives and things.
Even the opening credits feature Dexter doing such evil acts as... shaving, cooking breakfast and flossing.
In Game of Thrones, the murderous, incestuous twins Jaime and Cersei Lannister are seen doing such terrible things as having breakfast with their family, giving their condolences to a grieving mother, and giving friendly advice to a young man about to leave home for the first time.
Later, their father Tywin is first encountered skinning a deer, having presumably killed it during an earlier hunt. In a deleted scene from the third season, he also takes a break from plotting the downfall of his enemies and keeping his obnoxious grandson in line to spend the afternoon fishing.
Lord Locke and his men, when not raping their captives or hacking their limbs off, enjoy singing to pass the time while on long journeys.
True Blood - in Season 2, Eric tracks down Bill shopping for clothes for his new progeny (and provides some help). In the Season 5 premiere, we don't get to see Pam go to Walmart for her yellow sweats, she's characteristically vocal about how much she hates it.
Pretty much the whole premise of The Sopranos. And they're always eating!
In The Prisoner episode "The Schizoid Man," Number Two is shown getting a back massage from the Butler.
The 2012 German TV film Rommel features a scene where Hitler is waiting on a briefing regarding the Normandy invasion...by sketching.
In the Netflix series House of Cards (US), Frank Underwood, an amoral, ruthless politician without a moral compass, spends his downtime playing video games to let off steam. Significant subplots are focused on his favorite restaurant, his childhood memories, and his relationship with his wife: all of which humanize the otherwise monstrous Underwood.
Gotham: Carmine Falcone, ruthless crime lord of Gotham who runs his empire with an iron fist, apparently enjoys spending his free time feeding birds in the park like any other old man.
His main rival, Sal Maroni, is frequently seen enjoying meals in a restaurant he apparently owns.
Power Rangers Jungle Fury has an episode where Camille is feeling bummed at being pushed aside by Dai Shi during one of his training sessions. So as to find something to take her mind off it, she actually disguises herself and visits the pizza shop where the rangers all work.
Pretty much anytime Regina is out and about in public in Once Upon a Time. Her fairytale persona is the Evil Queen and in the real world she's the town mayor. Despite the countless deaths she's caused and how many times she's backstabbed and double-crossed the heroes she still casually walks about town and converses with them, albeit tensely.