Black Widow is one of Marvel's oldest characters and earliest Avengers. She was originally an Iron Man villain and even introduced Hawkeye to the Marvel Universe by making him an associate to her schemes. She later redeemed herself and became a member of the Avengers, S.H.I.E.L.D., and the Champions.
Natasha has had a very long life thanks to the biological tampering of the Red Room. She has had many ups and downs in her career, and she was a dedicated hero through most of it. She's also had the chance to make many friends and romances, but those bonds have led to plenty of heartbreak as well.
10 Hawkeye Breaking Things Off With The Black Widow
One of the first steps to Black Widow's turn from villain to hero was her relationship with Hawkeye. They became romantically involved during their criminal tenure. However, Clint wasn't happy with a life of crime.
Eventually, he broke things off with Black Widow when he tried to retire from his criminal career and joined up with the Avengers during the "Captain America's Kooky Quartet" era.
9 Breaking Things Off With Daredevil After Years Together
Black Widow and Daredevil were deeply romantically involved for years. Their relationship was so long-lived that the Daredevil comic became Daredevil and the Black Widow for a time. Natasha knew Daredevil's real name, and the two even moved to San Francisco together. However, things began to decay, and Natasha eventually broke things off with Daredevil.
They remained friends, and they even tried to rekindle things a few times over the years, but they never recaptured what was lost.
8 Visiting Daredevil Shortly After The Death Of Karen Page
Black Widow returned to Daredevil a few times during the Marvel Knights: Daredevil written by Kevin Smith, David Mack, and then Brian Michael Bendis. During Smith's time on the book with artist Joe Quesada, Daredevil was trapped in a deranged scheme conjured by Mysterio.
This involved Mysterio hiring Bullseye to sew further havoc in Daredevil's life. Karen Page had just recently returned at the time, and she was killed while trying to protect a wounded Daredevil from Bullseye. Black Widow had also returned to Matt's life at this point, and she was a shoulder to cry on while Matt mourned his lost love.
7 Yelena Belova Being Turned Into The Super-Adaptoid
Yelena Belova, the other Black Widow, was first brought onto the scene to help Black Widow in a plan eerily reminiscent of the Nic Cage and John Travolta classic, Face/Off. However, Yelena turned into a bit of an antagonist shortly afterward. She ended up in an illegal Vibranium mining operation where she was badly wounded by Sauron, and she was offered a new start by A.I.M while recovering.
This new start came in the form of a cybernetic upgrade to become the new Super-Adaptoid, an entity that can copy the powers of any hero she comes in contact with. Unfortunately for Yelena, she was never herself from this point onwards and only a pawn in the plans of A.I.M. and other villains.
6 Being Taken Into The Red Room In The First Place
The Red Room is a tragedy in itself. The Soviet Union took in young girls to become part of the Black Widow Ops Program, brutally training these young girls to become living weapons in the service to the USSR.
Natasha Romanoff, Yelena Belova, and countless other girls were trained in the Red Room, often by the Winter Soldier himself. The fallout from the Red Room has never left Natasha, and it still haunts her to this day.
5 When She Had Her Memories Wiped And Was Pitted Against Winter Soldier
After Bucky Barnes had the Soviet programming purged from his head by Captain America, he and the Black Widow struck up a relationship. Unfortunately, a man named Leo Novokov, who was also trained in the Red Room, kidnapped and brainwashed Black Widow to serve him.
Bucky had to enlist the help of Daredevil, Hawkeye, and Wolverine to save Natasha. Even when they gave her memories back, she had no memory of her relationship with Bucky. Later, this was remedied as well, but things were never really the same for Nat and Bucky again.
4 Being Forced To Kill Her Foster Father, Ivan Petrovich
For much of her superhero career, Black Widow had the support of another Russian by the name of Ivan Petrovich. He was like a father to Nat when she was younger, and he defected to America alongside her. Natasha valued Ivan's friendship and help greatly.
However, Ivan apparently wanted a romantic relationship with Natasha. Being spurned by her drove him off the deep end until he did the logical thing and became a cyborg bent on destroying the world. This forced the Black Widow to kill Ivan to stop his scheme.
3 When She Was Killed By Hydra Captain America During Secret Empire
When the Hydra-corrupted duplicate of Captain America took over the United States on behalf of Hydra, the Black Widow was one of the most stalwart resistance fighters. She fought hard to overthrow the Hydra regime, and this earned the ire of Hydra Cap.
In a showdown between Hydra Cap and Spider-Man Miles Morales, Black Widow saved Miles from taking a lethal blow from Hydra Cap's shield. Black Widow died saving Miles, and he was able to retreat with the help of the Wasp.
2 Discovering The New Black Widow Is Just A Clone And The Original Is Still Dead
Shortly after the Secret Empire event, rumors of Black Widow being sighted alive and well across the world became pouring into the Avengers database. Hawkeye and Winter Soldier, though far from friends, teamed up to investigate these sightings.
They did end up finding Black Widow, but she wasn't acting like herself. Clint and Buck discovered that the Red Room had returned, and Natasha was working tirelessly to bring it down. Furthermore, this Natasha wasn't the original. She was a clone that the Red Room had grown, but she had retained the memories of the prior Black Widow thanks to Soviet hero Ursa Major.
1 The Death Of Yelena Belova At The Hands Of Natasha Romanoff
When the Red Room returned, Yelena Belova apparently became involved with the program yet again. The Red Room had also cloned Yelena several times, and the new Natasha began using these clones as pawns.
However, Natasha had no use for Yelena and indeed saw her as an obstacle to her plans, and Natasha killed the original Yelena Belova.