In its 91 year history, it is for the first time that the perfume is being endorsed by a male celebrity, reported Daily Mail.
Pitt, 46, has reportedly got USD 7 million paycheck for the job.
The luxury brand has released a selection of teaser shots of the advertising campaign, due to hit magazines' November issues.
Chanel has also released a number of mini videos - a maximum of just eight seconds each featuring father-of-six.
Director Joe Wright, whose previous works include two Keira Knightley movies 'Atonement' and 'Anna Karenina', shot the full commercial.
Previously Marilyn Monroe, Nicole Kidman and Audrey Tautou have endorsed the perfume.