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I feel if you have the right script and decent character development then I see no problem with using more than one villian in a movie look at The Nolan Batman films they always had two or three villians pure movie and people love those films and the reason why those films work is because the villians have some kind of relation to eachother for example The Joker is responsible for the creation of Two Face I didn't see how Venom and The Sandman fit together in Spider-Man 3 apart from teaming up without even having any screen time before that scene
Green Goblin may not be part of the team, maybe he just puts the team together.
Doctor Octopus
Mysterio
Vulture
Kraven
Sandman
Electro