A new 30-second ad campaign for the iconic women's perfume is to be unveiled online via the French fashion house's YouTube page at 8:00 am (0600 GMT) Friday and then on television later in the day.
The decision to choose Pitt to head the campaign was announced back in May.
After campaigns depicting actress Estella Warren as red riding-hood, Kidman running through the streets of New York and actress Audrey Tautou aboard a luxurious night train, the sparse black and white in which Pitt appears marks a stark change.
In the ad, made by British director Joe Wright, Pitt recites a poem, specially written for the campaign, to a mystery woman.
Chanel sees the ad campaign as a new direction, saying that the perfume "has to go where we are not expected".
Press reports have said that Pitt is being paid seven million dollars (5.5 million euros) for his efforts.
No. 5 was created in 1921 by French perfumer Ernest Beaux, under the direction of Coco Chanel, who wanted a fragrance to complement her clothes.
The most famous face of the perfume was Marilyn Monroe, who in 1953 said it was all she wore to bed.