Valentina appears in the last episode where she meets John Walker who has just lost his title as Captain America. She recruits him and gives him the new title of US. Agent, stating the government are going to need a U.S Agent, not a new Captain America.
Valentina appears in this movie, during the post-credit scene where she is seen morning Natasha Romonoff, who had sacrificed her life so the Avengers could require the Soul Stone to use during the time heist, to bring back the dusted victims. While mourning, Valentina is asked by Yelena Belova as to why she is bothering her on her day off. Valentina mentions to Yelena that she has found the man whom she is claiming is responsible for Natasha's death. Valentina shows Belova the photo, which leads to the Black Widow hunting down the retired Avenger over Christmas time.
In 2025, Valentina learns of the rising tensions between Wakanda and the United States, specifically for the vibranium and hires her ex-husband Everett Ross to look into the case of the attacks on a local bridge. Valentina believes the Wakandians are responsible for the damage done to the bridge, while Ross isn't so sure. They ride back to Langley together where they discuss their former marriage and she becomes uncomfortable after hearing him talk to seemingly his new girlfriend. De Fontaine later arrives at Ross' house and arrests him for helping the Wakandians, by breaking into his house, and sending him to prison until Okoye, a former member of the Dora Milaje, breaks him out.
De Fountaine appeared in this show as one of the main characters.
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Valentina was supposed to appear in the MCU in iconological order, where she was meant to make her debut in Black Widow before The Falcon and The Winter Soldier, but the projects got swapped around due to the 2019 Coronavirus pandemic.