Captain Michael Sheen said that the American comedian, who will play in the striker role, is the team's "secret weapon".
Sheen said: "It's a real treat to have Will Ferrell playing for us. We're all big fans of his work but I don't think people realise he's a real serious competitor.
"Seeing him out there on the pitch today, he knows what he's doing. So I think he might be a secret weapon for us."
Scottish TV chef Gordon Ramsay said: "Everyone's impressed with Will Ferrell - he's played brilliantly well this morning - looking almost like our Peter Crouch but with a little bit more umph!"
Irish comedian Patrick Kielty, meanwhile, compared Ferrell to Liverpool target man Andy Carroll, later describing Ferrell as a "very strong lad" with "very bad hair".
Soccer Aid 2012 kicks off on Sunday at 6pm on ITV1.
> Donate to Soccer Aid and UNICEF through the official page here
Watch a recap of Soccer Aid through the years in the clip below:
Both teams in full:
England
Captain: Robbie Williams
Team: Jason Isaacs, Mark Owen, Marvin Humes, Aston Merrygold, Olly Murs, John Bishop, Jonathan Wilkes, Ben Shephard, Jamie Theakston and Paddy McGuinness.
Football legends: Teddy Sheringham, David Seaman, Kevin Phillips, Des Walker and Martin Keown.
Coached by Bradley Walsh.
Rest of the World
Captain: Michael Sheen
Team: Will Ferrell, Gerard Butler, Mike Myers, James McAvoy, Patrick Kielty, Sergio Pizzorno, Gordon Ramsay, Woody Harrelson and Edward Norton.
Football legends: Edwin van der Sar, Roy Keane, Ruud Van Nistelrooy, Hernan Crespo and Jaap Stam.
Coached by Kenny Dalglish and Ian Rush.
