The new adverts were shot by photographer Mikael Jansson.
In true Hollywood style, the campaign is said to have a cinematic feel that hints at the power and seduction of the Jimmy Choo woman.
"I'm such a great admirer and feel enormously honoured to be working with Nicole Kidman," Choi said.
"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 acted as a brand ambassador for Omega watches and Chanel No. 5 fragrance.
The 45-year-old is also set to take part in the eight person jury at this year's Cannes Film Festival.