Issue: Tales of Suspense # 57
Writer: Stan Lee
Artist: Don Heck
Publication Date: September 1964
Tony and Pepper go on a date, albeit accidentally. Whilst there, Iron Man saves lives, while new character Hawkeye(!) gets ignored. This is really all it takes to get Hawkeye to become a "super villain."
Hawkeye and his bag of arrows break up a bank robbery (not very villainous), but then it is assumed that he was the robber. Black Widow swings by in a moment of impeccable timing, and the two team up. Hawkeye has a massive crush on Black Widow, professing his love at one point. He escapes with her at the tale's end (after tussling with Iron Man, of course), but we'll surely see more of them soon. Kind of a humble beginning for what will go on to become one of the more famous members of the Avengers.
Favorite Panel: The first appearance of Hawkeye
Next: Tales to Astonish # 59