The Three Lions opened the scoring through a Mark Wright thunderbolt before second-half substitute Dimitar Berbatov netted twice in quick succession, the second from the penalty spot.
Jermain Defoe netted with a fine finish on the hour mark before striking the winner following a good combination move with Kieron Dyer.
The biennial charity match raises money for UNICEF UK through ticket sales and public donations, having being founded in 2006 by singer-songwriter Robbie Williams and TV presenter Jonathan Wilkes.