Marvel United: Return of the Sinister Six
Buy this firstBGG and Reddit posters name it the best Season 1 expansion; BGG rates it 8.66 from 725 ratings. It is a Kickstarter exclusive, out of print and pricey, with no heroes.
Needs: Needs a Marvel United core box: the original Marvel United, or another Marvel United core box such as Marvel United: X-Men.
Adds: Six new villains: Doctor Octopus, Electro, Kraven the Hunter, Mysterio, Sandman and Vulture. Each can be fought alone, or all six together in the Sinister Six Mode.