When the Black Widow first met the Winter Soldier, he was a man without a name, brainwashed into absolute loyalty to his Soviet masters. She too was a loyal soldier, fascinated by the apparently emotionless young spy. Guided by her conscience, she saw past the brainwashing, and found the soul of a good man deep within the Winter Soldier. It broke her heart to leave him behind when she left her life as a Soviet spy. When he reappeared, his bondage to his old masters had finally been broken by Captain America. She was more than happy to team up with him once again, this time as part of the Avengers.