Angelina Jolie for Nicole Kidman in Mr. & Mrs. Smith (2005)
The Smiths were initially to be played by Nicole Kidman and Johnny Depp, but both pulled out. Brad Pitt wanted to play the Mister, but hoped that Kidman would come back to be the Missus; instead the filmmakers secured the services of Angelina Jolie. Could Brad Pitt get on board with that? Oh yes, could he ever.