Ms. Marvel, Hulk
Ms. Marvel and Hulk unlock in the first few hours of the game. These Marel heroes will become available after players have rescued Jarvis in the single-player campaign. After that, players have to complete the “Snowy Tundra” mission and then Ms. Marvel and Hulk will be unlocked.
To unlock Iron Man, players have to progress through the campaign and complete the House Call mission. Complete the missions and Iron Man will become available for the rest of the game modes.
To unlock the Black Widow, players need to play the single-player campaign until they rescue Ms. Marvel in the mission To Stand Alone. After the mission is complete, follow the objectives on the carrier until a notification tells you that Black Widow is now available.
Thor is unlocked late in Marvel’s Avengers campaign. Players have to play the game until the mission “Testing…1…2..3”. Complete the missions and the hero will be unlocked.
Crystal Dynamics has saved the best Marvel hero for the last. Captain America can be unlocked after completing the mission “Testing…1…2..3”.