So you just saw Captain America: Winter Soldier and now you are intrigued by Black Widow, and interested in her stories, but you are new to comics?
These are good places to start, with excellent and self contained stories that won’t leave you scratching your head. Also none of these stories will make you cringe with silly sexism, a common problem in comic books.
1. Devin Grayson’s Black Widow: The Itsy Bitsy Spider and Breakdown
After many years of barely appearing in comics, writer Devin Grayson helped reintroduce her in 1999 with these two excellent miniseries. These redefined her as a more badass heroine in morally ambiguous espionage stories, and also introduced a villainous Black Widow, Yelena Belova. Both get to face each other in unexpected ways. Very good reads, very good art by JG Jones and Scott Hampton.
2. Marjorie Liu’s Black Widow: The Name of the Rose
With her cinematic debut in Iron Man 2, Marvel tried to give her an ongoing series in 2010. The first five issues by writer Marjorie Liu and artist Daniel Acuña are arguably the best Widow story ever made, with enough action and melodrama to make everybody happy. Secrets of the past, some guest stars from the Marvel Universe, and a striking finale. Very very recommended.
The series lasted three more issues with other creators but they never closed the following storyline due to cancellation.
3. Nathan Edmoson’s Black Widow: The Finely Woven Thread
And of course, since she got such an extended role in Captain America: The Winter Soldier, Marvel is trying again with a new ongoing series. As of now, five issues have been released, with very nice modern espionage stories. Writer Nathan Edmonson and artist Phil Noto are doing a great job, and it’s very worth checking.
A note about buying digital comics: both Comixology and Marvel Digital sell them, and if you have accounts on both they sync, so you get the comic you bought in both reader apps. Some (not all) paper comics and collected editions have a code that lets you get the digital comic for free in the Marvel Digital store, which is a nice bonus.