The deal lasts until 2010 and means that the snack firm, which uses former England football captain Lineker to front its advertising, will be the exclusive supplier of crisps and other bagged snacks at the new stadium.
Jon Goldstone, Walkers vice-president of marketing, said that the deal is part of an ongoing strategy to align the brand with sport.
Walkers is already the sponsor of Coca-Cola Championship side Leicester City FC, which plays at the Walker Stadium cementing its links with Lineker, a former Leicester player.
Jonathan Gregory, Wembley's marketing and commercial director, said: "We're delighted to welcome Walkers to our team of official suppliers, as we know that Walkers and sports fans have a long-standing history together."
Other recent promotional link ups involving Wembley have included a competition launched by Npower in January, offering seats in the stadium worth around £18,000 over ten years.
Last month Carlsberg, an official sponsor of the England football team, launched an on-pack promotional campaign offering season tickets to sporting and music events staged at the stadium.