Sure he wears a purple cape and a fishbowl on his head, but Mysterio's special effects-based powers make for a really trippy introduction to Disney Infinity: Marvel Super Heroes's Spider-Man playset.
Mysterio's made his way into plenty of Spider-Man video games — he was the main villain in the Questprobe Spidey game, after being passed over for Norman Osborn in the Atari 2600's web-based game. I'm not saying he doesn't show up regularly. I'm just saying he's not being used to full effect.
Disney Infinity: Marvel Super Heroes really makes the most of Mysterio. Not only is he featured prominently in the opening sequence to the Spider-Man playset adventure, there's an incredibly cool mission later on involving giant dice that's just classic Fishbowl Head.