Avengers (1963) #270
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Earth's Mightiest Heroes joined forces to take on threats that were too big for any one hero to tackle. With a roster that has included Captain America, Iron Man, Ant-Man, Hulk, Thor, Wasp and dozens more over the years, the Avengers have come to be regarded as Earth's No. 1 team.
Despondent and hopeless after it was discovered that she was not, in fact, Spider-Woman, Mary MacPherran encountered Doctor Doom, who offered her a chance to become superpowered in exchange for joining his army, to which Mary readily agreed, and Doom transformed her into Titania.