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.
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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