She will be promoting the spring/summer 2008 range for Marks & Spencer's Limited Collection -- a more upmarket line for the retailer. Cole will also join the other celebrity models for an advertising campaign, due to appear early next year.
Cole first appeared on the cover of Vogue at 16, and made headlines when she secured a place at Cambridge University to study social and political sciences at King's College.
She is known for her commitment to environmental issues and was stung by criticism of her decision to become the face of diamond company De Beers -- she has since refused to model for the company again.
Steve Sharp, executive director for marketing at M&S, said: "Her striking beauty goes without saying and her commitment to environmental issues makes for a great partnership with M&S."
Womenswear sales at M&S have risen on the back of a high-profile TV campaign featuring Twiggy and O'Connor alongside Noemie Lenoir, Elizabeth Jagger, Laura Bailey, Myleene Klaas and, for Christmas 2007, Antonio Banderas.
The campaigns are created by Rainey Kelly Campbell Roalfe/Y&R.
Separately, M&S has said that it will be introducing a J-cup size to its bra range for the first time, saying that demand for bigger sizes exists. It will go on sale online for a trial period.