The 40-year-old supermodel fronts the campaign for the British label's spring/summer 2014 collection, which aims to ''capture the iconic British model as an otherworldly woman in a darkly surreal environment'', according to the fashion house.
In a short film captured by photographer Steven Klein in East London, Kate is almost unrecognisable with a short yellow crop.
Steven was inspired by the 1960s British thriller, 'Peeping Tom', where a serial killer murders women and uses a camera to record their dying expressions - terrified looks of horror.
In the sinister short video Kate enters a desolate house, walks up a flight of stairs before removing her jacket and the series of shots have been captured to make it look as though somebody is watching her.
She struts around in dark, eerie surroundings and is seen clutching a small doll which is styled to replicate her own outfit and style.
Kate has had a longstanding relationship with the luxury brand but this is the first time she has starred in their ad campaign.
The supermodel was friends with of the brand's late eponymous founder and memorably appeared as a hologram during his autumn/winter 2006 show.
The movie begins filming in the UK.
The 'Sherlock' and 'Doctor Strange' star joined Gilmour onstage at the Royal Albert Hall for a rendition of the Pink Floyd classic.