The actor is the first ever man to advertise the cult French fragrance
Brad Pitt will front the campaign for Chanel No 5, one of the most popular perfumes for women.
Previous famous faces who have endorsed the fragrance include Nicole Kidman, Marilyn Monroe and Catherine Deneuve.
Pitt is said to be getting paid a seven-figure sum to appear in the ads and the campaign is being shot in the UK, where the Pitt-Jolie family is taking up residence over the summer.
Brad and Angelina have in fact purchased a £10m property in Richmond, south-west London, as they both have filming commitments in England over the next few months.