The deal, which is in partnership with Twentieth Century Fox Consumer Products, will see the introduction of a new co-created line of Chelsea-branded merchandise featuring the show's main characters - Homer and Bart Simpson.
Chelsea chief executive Ron Gourlay told the club's official website: "We are very pleased to announce such an exciting partnership.
"The Simpsons is a hugely popular show and I hope Chelsea fans will enjoy seeing its main characters in our colours."
Chelsea players Petr Cech, Eden Hazard, Frank Lampard, John Terry and Fernando Torres were all 'Simpson-ised' to celebrate the announcement.
Terry said: "It's great to see myself and the other players as Simpsons characters.
"The Simpsons was and still is my favourite show, and is now my kids' too. I can't wait to see what Bart and Homer will look like as Chelsea players."