The three-year deal with the Football Association will run until the end of the 2010 World Cup in South Africa. The England squad will showcase their M&S suits, designed by British tailor Timothy Everest, before the first England match at the new Wembley Stadium in London.
England captain John Terry said: 'We are extremely pleased with the outcome, as well as the look and feel of the suits.' Replicas of the suits will be on sale to fans, for about£400.
The high street chain will also provide outfits for the men's under-21 side and the England women's team.