Moss was picked to appear in the campaign by Stefano Pilati, YSL's creative director, after Brazilian model Gisele Bundchen fronted a similar campaign during last year's autumn and winter season.
The marketing activity includes press ads and a 24-page magazine called The Manifesto designed as a showcase for the campaign images.
The magazine will be distributed free throughout London and Milan, on 23 and 24 February in a selected number of street locations.
New York and Paris will follow on 27 February, Tokyo on 24 February and Hong Kong on 19 April. More than 1m copies will be distributed worldwide.
Other elements of the campaign include a travelling public installation of life-size images from the magazine that will begin at the Old Truman Brewery in Shoreditch on 23 and 24 February.
A behind-the scenes Manifesto video will also premiere on 25 February, exclusively at YSL.com.
Three seasons ago, Moss appeared in 14 marketing campaigns, but she has decided to be more selective this year.
She is currently appearing in campaigns for Donna Karan and make-up brand Rimmel.