The Homestar Runner cartoon Cheat Commandos: Shopping For Danger! revolves around this premise. The villainous Blue Lasers are at the supermarket, picking up their groceries, which the Commandos assume must be part of some sort of plan to "make it snow at the beach". It turns out that they're half-right; the Blue Laser Commander was convinced that the mildewy grout in his shower was the reason his organization couldn't crush the Cheat Commandos.
Pretty much the idea for Strong Bad Email; when he isn't antagonizing Homestar, Strong Bad answers emails from his fans. Heck, Strong Bad in general is pretty much the epitome of this trope, if you still consider him a villain. He's been seen shopping at Bubs's Concession Stand, regularly invites the other characters over to his house, goes fishing and a whole bunch of non-evil, non-villainous things.
Legendary Frog's cartoon "The Return of Ganondorf" has Ganondorf come back after being defeated by Link, claiming to have reformed. Link doesn't believe him though, so he keeps trying to spy on Ganondorf to catch him being evil, but only succeeds in seeing him playing Saria's Song, getting a drawing from him after sneaking into his room, and watching him at Zelda's slumber party as everyone does the Chicken Dance.