The supermodel wears the brand's famous bunny ears and black leotard along with heels and a fluffy tail as she strikes a sultry pose on the cover.
Inside the magazine, Kate features in an 18-page spread that sees her posing for a series of artful semi-nude snaps, shot by fashion photographers Mert Alas and Marcus Piggott.
Wearing a masked set of bunny ears, the fashion icon is stunning in the saucy shots.
In the interview accompanying the pictures, Kate opens up on her rise to international stardom.
"I was, like, a child when I started," she said. "I was 14. If it hadn't happened, I don't know what would have happened to me. I would be in Croydon working in a bar, probably.
"I wanted to be at the centre of things. I love working with creative people, and there was none of that where I came from. As soon as I was given a chance I took it."
Playboy's editorial director Jimmy Jellinek spoke about Kate appearing in the special issue. "Playboy's anniversary edition is a testament to 60 years of beautiful women, discerning taste, sexual emancipation, ground-breaking fiction and world-changing journalism," he said.
"Having Kate Moss, a global icon and the most important supermodel of the past 25 years, appear on our cover makes this issue the perfect way to launch Playboy's next 60 years."