Pitt, 48, will shoot his first campaign in London this week and will reportedly receive a seven-figure sum for the advertisements that will be released near the end of this year, reported E online.
The actor will make history as the famous fragrance's first male model.
Pitt will follow stars like Catherine Deneuve, Nicole Kidman, Lauren Hutton, Estella Warren and Ali MacGraw, who have also represented the women's scent.