Spider-Man: Season 1, Episode 20
Sting of the Scorpion/Trick or Treachery (20 Jan. 1968)
The Flys, a.k.a. the Patterson Twins, are paroled and freed. However, Spider-Man does not believe this and for a reason: they are framing him for all the heists they've done. It's up to Spidey to catch them in their act.