The pair were joined by veterans including Chris De Burgh, Nik Kershaw and Midge Ure and stars such as Julian Lennon, Cerys Matthews, Alison Moyet, Tim Minchin and Joss Stone at the concert hosted by Patrick Kielty to raise funds for the charity.
Although both Nik and Midge were content to play as part of the house backing band as guitarists, they both stepped forward to play their own hits, with Nik belting out 'Wouldn't It Be Good' while Midge performed 'Dancing With Tears In My Eyes'.
Cerys Matthews performed Catatonia's 'Road Rage' followed by covers of classic tracks 'Ring of Fire' and 'Love Me Tender'.
Julian Lennon closed the first half with an emotional rendition of 'Stand By Me' which he dedicated to his father, Beatles legend John Lennon.
The second act got off to a rousing start with classical violinist Charlie Siem, who admitted he was an unusual addition to the bill.
Before launching into his take on Nirvana's 'Smells Like Teen Spirit', he said: "You're probably wondering what someone with a violin is doing here so we're going to play something more in keeping with the spirit of The Rock theme."
Boy George later got most of the audience to their feet as he played his tracks 'Everything I Own' and 'Do You Really Want To Hurt Me?', before welcoming Chris De Burgh to the stage to play 'We Go To Africa' and 'Don't Pay The Ferryman'.
Joss Stone then put on a stunning performance including 'Super Duper Love', which prompted Midge to say: "We always knew this girl was talented and as older men we also realised she is extremely attractive!"
Pete Townshend then played five acoustic tracks including 'I'm One', 'Acid Queen' and 'Won't Get Fooled Again' before everyone who had performed took to the stage for a rousing rendition of David Bowie's 'Heroes'.
The Prince's Trust Rock Gala will be broadcast on Sky Arts and Sky 3D at 9pm on Christmas Day (25.12.11).