The supermodel was stunning in a beaded cape and her trademark black skinny jeans. She was flanked by husband Jamie Hince, having arrived in a black cab emblazoned with one of Kate's famous ads for the brand.
She was joined by fellow Rimmel faces Rita Ora and Georgia May Jagger. Pop sensation and Cara Delevingne's BFF Rita looked on trend in a full tartan suit by Moschino.
She completed the look with a bow tie and her trademark red lips.
Rita took to the stage to perform her biggest hits including R.I.P. and Shine The Light.
Georgia, meanwhile, had adopted an entirely different look. The daughter of Mick Jagger and Jerry Hall was channelling the 20s in a beaded, flapper-inspired dress. Dramatic green eye make-up and crimped hair finished off the super glamorous look.