The Oscar-winning actress will star in the luxury brand's autumn/winter 2013-2014 campaign.
The imagery was shot be photographer Mikael Jansson last month, and is described as having "a cinematic feel that hints at the power and seduction of the Jimmy Choo woman".
The advertisements will debut globally this August.
Kidman said of the news: "I've always loved fashion and often use it as a way to get into character. There is a lot of complexity, mystery and femininity to the Jimmy Choo woman."
Sandra Choi, creative director of Jimmy Choo, said: "I'm such a great admirer and feel enormously honoured to be working with Nicole Kidman.
"Nicole is one of the finest actresses in the world, who I knew could convey the empowered glamour of the brand. But she is also so nuanced and refined; she brings an attitude of defiance, strength, sensuality and elegance.
Kidman has previously been the face of Chanel's No.5 fragrance and Omega watches.