The charity football match, which has been organised by Robbie Williams, takes place on June 6 at Old Trafford. It will be broadcast live on ITV1.
Sheen, whose film credits include Frost/Nixon and The Damned United, will line up alongside Gethin Jones, Boyzone's Ronan Keating, Joe Calzaghe and Heroes star James Kyson-Lee.
"I fully anticipate this to be the greatest moment of my life. The Rest of the World is a big place and to be Captain of it is a huge honour and one I take very seriously," said Sheen.
"I now have a team of specialists monitoring my every movement. And I have a lot of movements for them to monitor, believe me. For me to play alongside the likes of Zidane is an extraordinary honour and privilege and one I'm sure he never dreamed would be possible for him when he started off as a footie-mad kid."
Former Liverpool star Kenny Daglish and Ian Rush will manage the Rest Of The World squad, which also includes footballers Zinedine Zidane, Henrik Larsson and Jens Lehmann, cricketer Brian Lara, Westlife's Shane Filan and Nicky Byrne, comic Patrick Kielty and Gordon Ramsay.
Robbie Williams will be joined in the England squad by GMTV's Ben Shephard, TV presenters Bradley Walsh and Jamie Theakston, actor Damian Lewis, boxing star Ricky Hatton and ex-footballers Alan Shearer, David Seaman, Teddy Sheringham and Jamie Redknapp.
Gavin & Stacey star James Corden was confirmed as England's assistant manager earlier this year.
Tickets for Soccer Aid are on sale now.