In "Harley's Holiday", a "reformed" Harley actually does go shopping — and takes the pet hyenas for a walk. When she buys a dress at a clothing store, she leaves with the dress before the cashier can remove the theft alarm from it. The shoplifter alarm starts ringing and the security guard comes over to try to explain that the cashier needs to remove the tag for her, but Harley sort of... freaks out, thinking she was going to be arrested again. Hilarity Ensues.
Harley: I'm havin' a bad day! I'm sick of people trying to shoot me, ride over me and blow me up! ...I didn't get to keep my new dress, and I actually paid for it!
Also in Batman: The Animated Series, viewers are privy to humorous shades of domesticity in the relationship between the Joker and Harley Quinn. For example, after he kicks her out of the gang in "Harley and Ivy", he is unable to find his socks and forgets to feed their pet hyenas.
And then there's that Christmas episode where Harley and Poison Ivy kidnap Bruce Wayne and brainwash him to pay for all their Christmas shopping. Batman is not amused.
In the Superman crossover episode they team up with Livewire and hit the Mall. Harley and Ivy get a lot of these; they're like some kind of bizarre sitcom.
An amusing subversion: the episode with The Creeper has him tearing through a series of outfights in a shop while the bored woman at the till looks on. You thoroughly expect him to abscond with the clothes sans payment... except Batman traces his identity because he used his former self's credit card.
"Almost Got 'Im" mostly consists of the villains hanging out playing poker, drinking tea, and swapping Death Trap stories without being up to any evil schemes (except for the Joker...).
Also used in the episode 'The Waterbending Scroll', where the villains (well, Iroh, who isn't exactly a villain) do go shopping. It's later shown that the Lotus tile he was seeking to buy was really a secret password for the Lotus Society, thus he was actually trying to make contact with local operatives for his secret society.
Many of Iroh and Zuko's subplots in season two (e.g. Iroh starting up his own tea shop) could count as this depending on whether or not you regard them as villains at that point. The best example is Tales of Ba Sing Se, in which Iroh shops for a picnic basket and Zuko goes out on a date with an Earth Kingdom girl.
An important sub-plot during the third season when the Gaang infiltrated the Fire Nation was that the Fire Nation citizens were perfectly normal people. Aang went to school in one episode, and other than an unhealthy personality cult over their leader ("Here is a picture of Fire Lord Ozai. And here is one I made out of noodles!) and them being taught a falsified version of history (The Air Nomads had an army?) it was filled with the same cliques of nerds, jocks and bullies as any other school. Oh and unruly students were sent to reform school — by which they meant the coal mines.
Zuko infiltrated a high-security prison trying to free Sokka's dad and the rest of his tribe. He tries to get over some information.
Male Guard: Hey, newbie! I know it is regulation, but you can take off your helmet in the Lounge. Zuko: [Thinking quickly] But what if there is an incident? If I'm not prepared someone could sneak up on me and bash me over the head. [The male and female guard laughs their assess off] Female Guard: Give him a week; he'll loosen up. Zuko: So can the new guy ask a few questions? Female Guard:No, you can't date any of the female guards. Male Guard: Trust me, you don't wanna! [The Female Guard throws her cup at him, causing a third guard at the table to laugh up a storm.]
An episode of GIJoe opened with the Baroness just minding her own business at a spa. (Flint and Lady Jay had the day off too; unfortunately for all three of them and Cobra Commander, a third-party villain named the Gamemaster had other ideas...)
In an episode of Buzz Lightyear of Star Command, Buzz reacts to a string of mysterious disappearances by calling Emperor Zurg via videophone. Apparently, he was in a business meeting with every other recurring villain/henchman on the show, conveniently clearing them all. However, he adds that he DOES have some great plans lined up for the next fiscal year.
One episode of Codename: Kids Next Door has a literal example of this, where the heroes and villains are fighting over a box of breakfast cereal in the supermarket! (Making it even more bizarre, the supermaket is an exclusive place that caters only to villains.)
There also seems to be a coffee shop where all the villains of the series hang out, that was seen in Operation: F.L.U.S.H. The barista even wears a supervillain-style mask.
And in one episode, the Kids Next Door accuse Chad/Numbuh 274 for destroying a bunch of bikes. However, he was just doing a part-time job of being a pizza delivery man.
And Operation: A.F.L.O.A.T. started with the villains having a barbecue, and the only reason any trouble started was because Sector V decided to crash it.
Norm the Genie from The Fairly OddParents did this after becoming a fairy godparent, except it wasn't literal shopping. It was car racing, Hawaii, wish-granting, flirting, restaurants, etc. Probably because now that he was a Fairy, he had to follow their rules and laws, or risk losing his new status and freedom and going back to the lamp as a Genie.
The Thanksgiving storybook does this with Vicky, though it's technically her family (who we know she terrorizes on the show) doing the shopping. In this book, Timmy finds that Vicky is alone on Thanksgiving because her family went out to get cranberry sauce and their car broke down, and, for once, Vicky is actually worried for them.
In Freakazoid!, the titular hero has encountered The Lobe at least twice while the latter was shopping. He expresses amazement at this, saying "Lobe? I thought you were terrorizing [name of place] with some kind of [silly sounding weapon]!"
The Lobe decides he needs a break from villainy and goes to a restaurant, where everybody knows him by name, and he's their favorite guest. He does cut this short to help out Freakazoid, but demands a chase scene before he does so.
Queen Cobra is also shown having decorated her villainous lair with Chinese Lanterns, as per Freakazoid's suggestion, off camera, sadly.
The trope is used in the Gargoyles episode "Her Brother's Keeper" where Elisa Maza shadows David Xanatos from the air while the villain is driving in order to get something incriminating on him. Unfortunately, Xanatos is well aware that Maza is following him and casually notes "Let's go shopping" as a completely innocuous activity in order to frustrate her.
Invader Zim has at least two such events. In "Mortos De Soulstealer", Dib summons the titular demon to eat Zim's soul, but in order to regain enough power to do this, Mortos must prepare...by eating fast food, getting new pants, petting puppies, and hitting on a goth chick at the fair.
The whole episode "Zim Eats Waffles" is about this and Dib's inability to catch Zim being evil. Dib has a hidden spy camera in Zim's house, but rather than doing evil things, Zim...eats waffles and putters around like it's a lazy Saturday. His lazy Saturdays involve rampaging cyber-zombies and flesh-eating robot squid. Demon squid.
Later in the same episode, it turns out that Flash knows all about their little "hole-in-the-wall on Third."
A common plot has Kim Possible outright attacking a shopping villain for a crime they didn't commit. It doesn't matter if said villain should be in jail right now for what they did do in previous episodes.
Used repeatedly on Phineas and Ferb with Perry the Platypus and Dr. Doofenshmirtz (expected, as the two exist to parody every action and spy movie trope in existence).
In "Unfair Science Fair Redux", Perry and Doofenshmirtz go out shopping together to get supplies for Doof's latest Evil Plan—in the store, they encounter Perry's boss Major Monogram and his intern Karl, also out shopping. They stare at each other awkwardly and back away without saying anything.
One episode of The Powerpuff Girls had the Gangreen Gang using the Powerpuff Hotline and sending the girls after other villains. They arrived to find (in turn) Mojo Jojo sleeping (and reading the paper before that, they asked), Fuzzy Lumpkins bathing, and Him doing aerobics. After calling the mayor's office to complain, the three villains find out what happened, and beat the crud out of the Gangrene Gang.
In "Just Another Manic Mojo", Mojo Jojo spends the first half of the episode going out to buy some eggs for his breakfast. When he leaves the house without his wallet, he even resorts to...going back inside to get it. As opposed to stealing the eggs as a how typical villain might.
In "Meet the Beat-Alls", Mojo, Moko, Fuzzy, Princess, and Him are shown in a grocery store buying items that are all white.
Another episode had Him working at a pancake restaurant.
In the Father's Day episode Mojo is seen in his home building a ship in a bottle.
In the episode "Brother from Another Series," Bart laments his inability to know what his nemesis Sideshow Bob is thinking. Cut to Sideshow Bob, wondering whether they still make that shampoo he likes. Cue Jarring chord.
At the end of the same episode, when Bob is sent to jail with his brother Cecil, Chief Wiggum says "who knows what diabolical schemes they might concoct?" Cut to Bob and Cecil having a Wimp Fight over the top bunk. After losing, Cecil asks where the menus are.
At the beach, Chief Wiggum is told by his son to relax, since he's on vacation, to which he dramatically replies, "Crime doesn't take a vacation." Whip Pan to the Springfield Mafia throwing a beach ball around; one mobster plaintively cries "Careful, you'll pop it!"
A literal example in "The Old Man and Lisa" where after losing his fortune, Mr Burns has to shop for himself. Hilarity Ensues.
Another episode has Mr. Burns, during a lull in his evil scheme, casually asking Lisa how things are going with her in her life. She responds by angrily berating him on his diabolical plans, causing him to irritatedly remark that she never switches off, does she?!
Megatron of Transformers: Beast Wars tends to do a lot of this. At one point, we find him taking a nap in his command chair, but more notable and frequent is his habit of relaxing in a hot tub while he schemes. He even has a rubber ducky. As Megatron is both a Magnificent Bastard and a Large Ham, the rubber ducky itself has become something of an icon among the fans.
The episode Changing of the Guard of Beast Wars had Inferno deliver a report to Megatron while it was obvious Megatron had interrupted a game of cards between him, Waspinator, and Quickstrike.
WordGirl had a variation when, while fighting another villain, the heroine encounters recurring nemesis Dr. Two-Brains making his way home after a trip to buy crackers (which he will put stolen cheese on).
Another episode has Becky go shopping with her mother, only to find Tobey out shopping with his mother as well. Although in this case, he had an evil plan going at the same time. (Actually, Tobey's plans often grow out of him doing innocuous activities like this trope and just letting his temper get the best of him in the middle of doing it.)
Two-Brains pretended to be out shopping in "Rat Trap", but only because WordGirl had shown up before he could commit any of the planned crimes.
The Venture Bros. is particularly fond of this trope, since it often focuses on the after-hours activities of super-scientists and super-villains.
Most of the supervillains in the Guild of Calamitous Intent live in a gated community called Malice.
The leader of the Guild of Calamitous Intent is David Bowie.
"Hate Floats" has Phantom Limb and Dr. Girlfriend shopping for cutlery at the mall.
In "Tag Sale, You're It!", Dr. Venture has a yard sale, and every villain he's ever faced shows up. Granted, they are shopping for mad-science weapons and it's only a matter of time before a fight breaks out.
"Return to Spiderskull Island" features the old Team Venture gang and their former archvillains getting together at the titular island for Jonas Venture Jr.'s inauguration of the Jonas Venture Sr. museum. Team Venture is miffed that the villains seem to be making more table money selling autographs than they are.
When Rusty gets out of being arched for his group therapy night, Dean, Hank, Sergeant Hatred and the entire Monarch mook contingent go see a movie at the same theater. This a group that was attempting to murder each other mere moments earlier. The mooks even give Hank and Dean a ride home when Hatred leaves them there.
In "Showdown at Cremation Creek", The Monarch and Dr. Girlfriend invite a huge contingent of supervillains to their wedding. They all remain civilized, even after The Phantom Limb storms the cocoon with his death squads to steal Dr. Girlfriend back; most of the supervillains flee the scene.
In Danny Phantom, The Guys in White were briefly seen shopping in the mall before their sensors alerted them to Danny.
"Why do they call it a White Sale when none of the clothes are white?"
It's also been confirmed that Vlad Plasmius is a huge Green Bay Packers fan and presumably interrupts his evil scheming whenever there's a game on television.
Cinderella had Lady Tremaine giving a music lesson to her daughters.
101 Dalmatians has Cruella De Ville who likes shopping and visiting old school mates.
Beauty and the Beast has Gaston who does lots of things when he's not plotting evil such as decorating his place with antlers, taking part in spitting contests, drink beer with his buddies, and trying to play chess. And no one does any of those things like he does!
Young Justice: Tigress a disguised Artemis temporarily swaps her guarding position with a mook, telling the boss she needs some coffee. She goes into another room, where an unmasked faceless goon, nonchalantly offers her a "fresh pot."
Ben 10: Ultimate Alien: The gang ask Jimmy how to get in touch with the Forever Knights, he simply opens up a web-chat with one, who he plays a World of WarcraftExpy with. The Knight greets him, and seems friendly, but the lair collapses on him at that point.
Teen Titans: The Hive 5 get an episode around them, showing that they're incredibly immature, at one point almost all the members go off to build a pillow fort. Eventually they split up and go on a crime spree across the city. Kid Flash foils their robbery attempts one by one, and it eventually cuts to Mammoth exiting a convenience store with a candy bar. There's a blur of light as Kid Flash swipes the candy bar, followed by Mammoth angrily exclaiming, "I paid for that!"
Happens all the time with Rex and the Duke of Gawayn
In the SpongeBob SquarePants episode Spy Buddies, Spongbob and Patrick spy on Plankton to find out what he's up to and discover that he is... buying baby clothes.
Aku (On the phone): Yes, I can hold. (Sits complacently) Yes. I would like to place an order for delivery. Aku. I think I'm in the computer. YES! That's it. I'd like a large— what? Huh? EXTRA THICK!!! Thirty minutes or it's free? EXCELLENT!!! (Maniacal laughter which is cut off by the pizza guy hanging up)
In the South Park episode "Chef Goes Nanners", Jimbo and Ned infiltrate a Ku Klux Klan meeting, where they see the Klansmen go over last week's minutes, raffle off a cake, and play a game of "who's got the silliest thing on under their robe".