The model, 39, looks sensational in the image, which will feature in the publication's December issue. She is also said to have posed nude for the January issue, to mark her 40th birthday.
Playboy founder Hugh Hefner said the face of Rimmel and mum-of-one Kate was the perfect poster girl for the world-famous brand.
"She's a worldwide celebrity and iconic and crosses the boundaries from sexual imagery to upscale modelling," he said. "It's a natural for us."
Playboy's editorial director Jimmy Jellinek also sang the Croydon-born supermodel's praises. "This is a massive global brand," he said. "You need a global icon in order to celebrate that - that was the impetus.
"You're talking about the face of Burberry, the biggest supermodel in the world on the cover of Playboy. She's the perfect partner for us to help launch the next 60 years.
"It started with Marilyn Monroe on the cover of Playboy 60 years ago, an icon for her time. Now we've got Kate Moss!"