The French-based company announced Wednesday that the 48-year-old actor will star in an upcoming ad campaign for its signature women's scent. Other famous names who have been the face of Chanel include Catherine Deneuve, Nicole Kidman and Audrey Tautou.
Chanel's founding designer, the late Coco Chanel, also modeled in ads in 1937 for what is now the company's oldest fragrance. It remains one of the world's top-selling perfumes.
Pitt, a former People magazine Sexiest Man Alive, is engaged to long-time companion Angelina Jolie.