The 29-year-old track cyclist from Bedfordshire will be used by the brand renowned for its iconic ‘boy on bike’ ads in an attempt to align the Premier Foods bread to healthy-eating and education initiatives.
A Hovis spokesman said it was "likely but not confirmed" that the initial "six figure partnership" will result in the star athlete appearing in multimedia ad campaigns.
The bid to associate Hovis with a healthy lifestyle follows years of bread and other carbohydrates being attacked in slimming fads like the Atkins diet.
Jon Goldstone, marketing director of Hovis, said he was "delighted" with the new partnership with Pendleton, which he dubbed ‘Girl on a Bike’.
Last month, Hovis’ 122 second ad ‘Go on Lad’, created by MCBD to celebrate its 122 year history, was named ‘Ad of the Decade’ in a poll of ITV viewers.
Pendleton said: "I hope my work for Hovis will inspire a new generation of ‘girls and boys on bikes’ who enjoy cycling as much as I did when I was younger and maybe even inspire some champions of the future."