The two stars will captain the England and Rest of the World squads for the fourth series of the charity football event on Sunday, May 27.
Soccer Aid 2010 saw Williams's team lose 7-6 on penalties after a 2-2 draw. Hollywood star Woody Harrelson scored the winning penalty, and will return for this year's match.
The Take That star revealed that he is confident that England will be able to take home this year's trophy.
"Sometimes the English sense of politeness can stretch too far. As hosts, I think we made our guests too comfortable last time. Now it's time for some 1966-style passion. Good luck Rest of the World, you'll need it," he told The Sun.
Michael Sheen replied: "We can't wait to get at the England team again. We had them running scared last time and they bottled it in the penalty shootout. We've got a brilliant squad and everyone is really up for it. Bring it on!"
Hollywood stars Gerard Butler, Mike Myers, Jason Isaacs, Will Ferrell and Edward Norton will also take to the Old Trafford pitch later this month.
Tickets are now on sale for Soccer Aid 2012 - call 0161 444 2012 or visit itv.com/socceraid.
The Soccer Aid lineup so far is as follows:
Robbie Williams (Captain), Jason Isaacs, John Bishop, Paddy McGuinness, Olly Murs, Jonathan Wilkes, Ben Shephard, Jamie Theakston, Marvin Humes, Aston Merrygold, David Seaman, Jamie Redknapp, Teddy Sheringham, Mark Owen, Martin Keown, Des Walker, Kevin Phillips and Bradley Walsh.
Rest of the World:
Michael Sheen (Captain), Will Ferrell, Gerard Butler, Woody Harrelson, Edward Norton, Clarence Seedorf, Mike Myers, Gordon Ramsay, James McAvoy, Edwin Van der Sar, Ruud Van Nistelrooy, Jaap Stam, Patrick Kielty, Roy Keane, Hernan Crespo, Sergio Pizzorno, Kenny Dalglish (Coach), Ian Rush (assistant).
Watch a promo for Soccer Aid 2012 below: