Brad Pitt will make history as the famous fragrance's first male model.
According to E! Online, the 48-year-old actor will shoot his first campaign in London this week.
He will reportedly receive a seven-figure sum for the advertisements that will be released near the end of this year.
The father-of-six follows in the footsteps of stars including Catherine Deneuve, Nicole Kidman, Lauren Hutton, Estella Warren and Ali MacGraw, who has also represented the women's scent.
The star and his fiancée Angelina Jolie recently purchased a new home in the city he is to shoot the adverts in.
The Hollywood pair decided to buy the property - named Whornes Place - while renting it for over NZ$60,000 a month last year.
Pitt was filming zombie thriller World War Z last summer when they were staying in the capital city's borough of Richmond with their six children.
Watch Nicole Kidman in a Chanel No.5 ad campaign:
- BANG! Showbiz