The American blonde will feature in a brand new print and TV campaign, which will show black and white images of the actress and beauty icon.
The fashion and beauty house were inspired when they discovered an audio recording of a 1960 interview when Monroe speaks about cheeky response to Life magazine in 1952 when they asked her what she wore to bed.
"You know, they ask me questions. Just an example: 'What do you wear to bed? A pyjama top? The bottoms of the pyjamas? A nightgown?' So I said: 'Chanel No.5', because it's the truth," Monroe says in the 50-year-old recording.
The quote remains one of Monroe’s most memorable.
The No. 5 fragrance was launched in 1921 by Gabrielle Chanel and has been considered a perfume classic ever since.
The new Marilyn Monroe campaign is due to launch in December this year.
She will join modern stars Keira Knightley, Audrey Toutoe, Nicole Kidman and most recently, Brad Pitt as the face of a Chanel campaign.