I think this is the first time Black Widow has appeared in an Avengers comic with her updated, most well known look.
2014 - Captain America: The Winter Soldier | The Amazing Spider-Man 2 | X-Men: Days of Future Past | Guardians of the Galaxy
2015 - Avengers: Age of Ultron | The Fantastic Four | Ant-Man
2016 - Captain America 3 | Batman vs. Superman | X-Men: Apocalypse | The Amazing Spider-Man 3 | Doctor Strange
TV - Agents of S.H.I.E.L.D. | Agent Carter | Daredevil | Luke Cage | Iron Fist | Jessica Jones | The Defenders
TV - Arrow | The Flash | Gotham | Constantine | iZOMBIE