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I think the previous Black Widow thread got lost in the board crash, so I'm putting my thoughts down again.

She had first appearances in the pages of Tales of Suspense as an Iron Man villainess, then other significant appearances in Avengers, including the revelation of her previous marriage. (Precise issues for these significant appearances, anyone?) Then she had a solo stint as half a splitbook in Amazing Adventures (her first solo series), and she also served time as Daredevil's partner.

My own interest begins after these. With these done, I am looking into solo stories afterwards.

I locate the following:

Comic-sized:
Marvel Fanfare (vol.1) #10-13
Fury/Black Widow: Death Duty one-shot (prestige format/gluebound)
Journey into Mystery #517-519
Black Widow (vol.1) #1-3
Black Widow (vol.2): Breakdown #1-3
Black Widow (vol.3): Pale Little Spider #1-3
Black Widow (vol.4): Homecoming #1-6
Black Widow (vol.5): The Things They Say About Her #1-6

Oversized:
Black Widow: The Coldest War (Marvel Graphic Novel)
Punisher/Black Widow: Spinning Doomsday's Web (Marvel Graphic Novel)