Vision is the first Avenger besides Thor to lift Mjolnir in the MCU. The moment occurs in Avengers: Age of Ultron, when the newly activated android casually picks up Thor’s enchanted hammer and hands it to him.
Mjolnir is enchanted so that only someone deemed worthy can wield it. Earlier in the film, the Avengers try to lift the hammer as a party challenge, but none of them succeeds. Vision’s effortless action shocks the group because he has only just been created from the Mind Stone, vibranium, and the remains of J.A.R.V.I.S. His ability to lift Mjolnir immediately suggests that he possesses unusual moral purity and a distinctive relationship to the team.
The scene is sometimes confused with Captain America’s later success. Steve Rogers moves Mjolnir during the final battle in Avengers: Endgame, but that occurs after Vision’s first on-screen feat. Odin and Hela also interact with or lift Mjolnir in the MCU, but neither is an Avenger, and Hela’s destruction of the hammer occurs later in Thor: Ragnarok. Thus, among Avengers, Vision is the first after Thor.