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 $7 million (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.