Black Widow - The Sting of the Widow
Stan Lee, N. Korok, Gary Freidrich, Mimi Gold, Roy Thomas, Gerry Conway(writers), John Buscema, Sal Buscema, Don Heck, Bill Everett, Gene Colan(artists)
Collection of several early stories about her. The original comics were:
1. Tales of Suspense 52 - the first appearance with her going up against Iron Man.
2. The Amazing Spider-Man 86 - when she first encounters the webcrawler.
3. Amazing Adventures v2 1-8 - her first mini-series.
4. Daredevil 81 - Natasha meets and saves a drowning Daredevil and later fights alongside him against the Owl.