The 39-year-old model will feature in a short clip that runs for just over two minutes as part of the shoe designer's autumn/winter 2013 campaign, 'Made For Walking', with the video debuting at the brand's store opening in Milan, Italy.
The advertorial film sees the blonde beauty getting out a Rolls Royce, choosing to walk through the streets of London in nothing but a pair of thigh-high boots and white fur coat when she grows bored of waiting in traffic.
The black and white footage displays her strutting down the street to the soundtrack of Nancy Sinatra's famous song, 'These Boots Are Made for Walkin'.
In a shorter promotional video on Vogue.co.uk, Kate explains she is a fan of high boots as they cover up her long legs.
She says: ''When I wear boots especially if I'm wearing a short skirt, I think you feel like you might want to wear a heel but you'd wear them with a longer boot so there's not so much leg.''
The campaign marks the first time Kate has fronted adverts for the American shoe designer, who most recently designed the heels for Beyonce's 'Mrs Carter' world tour.
The supermodel replaces Natalia Vodianova as the face of the brand, following the Russian model's two seasons with the company.