The 32-year-old British supermodel, who first appeared as the face of Calvin Klein 14 years ago, will appear on billboards and in magazines this fall after signing a contract reported to be worth $900,000.
"Kate and the Calvin Klein brand have a long history together and it felt natural to reunite them for this new Jeans campaign, which will inevitably re-ignite that spark and highlight the sexy, cool essence of both Kate and Calvin Klein," said campaign creative director Fabien Baron.
The ads, which also feature British male model Jamie Dornan, will be shot in New York this week, Baron said.
It was the 1992 Calvin Klein commercials -- where Moss appeared in a series of black-and-white shots with a bare-chested Mark Wahlberg -- that made Moss a household name.
She continued to work with Calvin Klein until 1999.
Burberry and other fashion houses canceled contracts with Moss last year after a British tabloid published a picture of her allegedly using cocaine.
But she has secured a number of new contracts after she apologized and attended a rehab clinic.