The 30-second spot, "rebellious", for the launch of Rimmel's Extreme Definition comb mascara shows Moss causing havoc in a palace, where she is shown swinging from a lampshade, tearing down curtains, spraying champagne, and teasing a palace guard.
The spots, through J Walter Thompson-owned fashion and lifestyle agency Label, aim to bring out the model's wild side, after she calmed down following the recent birth of her baby Lila.
Label account director Kenny Hill said the spots aim to lose the beauty industry's image of unrealistic perfection.
"Girls are fed up with the over-retouched and unattainable visions of 'perfect beauty', peddled by much of the beauty industry. With Kate Moss and the London theme, we strive to produce work for Rimmel that is an antidote for that cynicism," Hill said.
Moss's image is particularly high profile at the moment, as she is featured pole-dancing in the video for Detroit rock outfit The White Stripes' new single 'I Just Don't Know What to Do with Myself', written by the legendary Hal David and Burt Bacharach and which was previously a hit for Dusty Springfield.
Moss is also featured in the current issue of Q magazine, interviewed by David Bowie, where she admits to having taken drugs.
"The key to capturing Kate's naturally playful and rebellious side was to get her to relax and just really enjoy herself on set, sometimes unaware that the camera was even rolling," Hill said.
The TV campaign will break on Friday September 5, followed by interactive work on Sky to follow on from Rimmel's previous successful interactive work with the channel.
A print campaign in the women's and style press will support the spots, featuring Moss in shots by Craig McDean.
Moss is one of the most recognisable faces in the world and is estimated to be worth £15m.
The campaign will also be used to launch the product globally from Germany to the US, where Rimmel is one of the fastest-growing cosmetic brands.
The campaign was written and art directed by Robin Harvey, Blaise Douglas and Richard Midgley and directed by Sean Ellis through RSA. Media planning and buying is through OMD.
In her interview in Q, Moss says that although she still drinks she no longer takes drugs.
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