Unlockable How to Unlock
Big Wheel
Keep choosing the bad choice when you asked by computer (after beating Tinkerer)
Black Cat
Choose to save Black cat when you fight her (pick the 1st choice when asked by Smythe)
Hobgoblin
Keep choosing the bad choice (the 2nd/3rd choice) before fighting Kraven
Jessica Drew
Choose to help Shield crew from the symbiote (before you fight with Jessica Drew)
Luke Cage
Make the bad choice (2nd choice) when you asked by a man who say he can divert the train containing symbiote
Random Assist
You can get mysterio, Night Crawler, Wolverine, Ctylok, Galactus, Hypno Hustler randomly by beating any level or buying the ultra rare powe ups
Shocker
choose to free Shocker after defeating him
Solidarity
Bring shocker to jail (after beating him)
Storm
Keep choosing the good answer when you asked by computer after defeating Tinkerer