The English starting XI included a few stars of their own, with Jamie Carragher, Sol Campbell, Phil Neville and Robbie Fowler joined by global singing stars Olly Murs and Robbie Williams.
With Leicester City's hero Claudio Ranieri at the helm of the Rest of the World side, they looked threatening throughout the first-half as Ronaldinho showcased his still immense talent.
But it was English television and radio presenter Mark Wright, who broke the deadlock with a spectacular free-kick in the 50th minute.
England were reduced to 10 men only four minutes later though, with television presenter Ben Shephard given a second yellow card, and former Tottenham Hotspur and Manchester United star Dimitar Berbatov cashing in.
His 56th minute strike levelled proceedings before Ronaldinho drew a penalty only three minutes later and Berbatov was on hand to put his side in front 2-1.
But there was yet another twist in this entertaining fixture with Defoe evading former Italy FIFA World Cup winning captain Fabio Cannavaro and scoring the equaliser in the 65th minute.
And it was Defoe, who showed he was a class above everyone else on the field as he bagged his brace and gave the England side a hard-fought 3-2 win.
Charity was the real winner though with £5,391,398 ($10.6 million) raised on the night for UNICEF to assist disadvantaged children around the world.
Incoming Manchester United manager Jose Mourinho was also on hand at "his new house" as the Portuguese tactician shared a moment with football icon Pele.