Oliver will feature in advertising and PR activity for Samsung as the brand seeks to encourage participation in its upcoming London 2012 marketing campaign.
Samsung has already signed up David Beckham and Zara Phillips as its Olympic brand ambassadors in order to drive awareness of its digital activity supporting the Olympic Torch Relay and blogger programmes for the Games themselves.
Oliver was brand ambassador for Paralympic Games' sponsor Sainsbury's for 11 years and ended his association with the supermarket in December last year with an ad featuring a montage of the campaigns he was involved in.
Meanwhile, Beckham has partnered with Sainsbury's as part of its Active Kids campaign, in a deal reported to be worth £5m.
Follow Matthew Chapman at @mattchapmanUK