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Black Panther (DLC character)

Cable (DLC character)

Captain America

Carnage (DLC character)

Daredevil

Deadpool (Complete the 'DC: Captol Offence' Level)

Gambit

Green Goblin (Complete the 'Wakanda: Panther's Lair' Level)

Hulk (Collect 5 Gamma Regulators) 

Human Torch

Iceman

Invisible Woman

Iron Fist (Unlockable via Story)

Iron Man

Jean Grey (Collect 5 M'Kraan Fragments)

Juggernaut (Originally a pre-order bonus, now available to purchase as a download)

Luke Cage

Magneto (DLC character)

Mr. Fantastic

Ms. Marvel (Complete the 'NYC: Missing Marvel' Level)

Nanite Nick Fury (Complete Story Mode)

Penance (Complete the 'Prison: Jail Break-In' Level)

Psylocke (DLC character)

Songbird (Join the Pro-Reg side)

Spider-Man

Storm

Thing

Thor (Collect 5 Asgardian Runes)

Venom (Complete the 'Wakanda: Panther's Lair' Level)

Wolverine