Pattinson will star in a TV ad and press ads for the luxury brand’s men’s fragrance later this year.
The campaign will run in Europe and Asia from September but is understood to exclude the UK, China and Japan.
Dior credited Pattinson’s acting in films such as Remember Me by Allen Coulter, Water for Elephants by Francis Lawrence, and Bel Ami as the reasons behind him being chosen to front the brand, rather than his more popular stint in teen vampire series the Twilight Saga.
Pattinson follows the footsteps of other Hollywood a-listers including Charlize Theron, Jude Law and Natalie Portman who have all fronted ad campaigns for the fashion house.
Print ads will be photographed by American artist Nan Goldin and the TV spot filmed by French director Romain Gavras.