Ronaldinho is the latest global star to confirm his involvement in the Uefa celebration game at Old Trafford on March 13th.
The two-time Fifa World Player of the Year will be joined by Barcelona team-mates Carles Puyol, Lilian Thuram and Gianluca Zambrotta in the Europe XI squad to face Manchester United.
The quartet will join an already star-studded line-up, which includes former England captain and United favourite David Beckham, Liverpool skipper Steven Gerrard and defensive colleague Jamie Carragher.
The side will be coached by Italy's World Cup-winning boss Marcello Lippi.
United boss Sir Alex Ferguson has already vowed to field his strongest possible line-up, which is expected to include Wayne Rooney and Cristiano Ronaldo.
Old Trafford legend Sir Bobby Charlton said: "It promises to be a fantastic occasion with Ronaldinho and David Beckham facing our Manchester United team.
"Every young football fan would relish the chance to see all these great players. It's one of those rare opportunities to see European football's finest players together on one pitch, and Old Trafford is the perfect stage."
The game will mark the 50th anniversary of both the Treaty of Rome and United's entry into European football and all profits from the match will go to the Manchester United Foundation, which aims to leave a legacy in local, national and global communities.
Thuram added: "I enjoy playing in this type of match, especially one that emphasises the role football can play within European society."