Prince of Darkness Ozzy Osbourne and rock band McFly have been signed up to play at the Prince's Trust Tower of London concert.
The stars will join the Prince of Wales, Prince William and Prince Harry and the Duchess of Cornwall to celebrate the charity's 30th birthday.
Surviving Bee Gees Barry and Robin Gibb, Pink, Annie Lennox, the Sugababes, Lionel Richie and Ronan Keating have already been announced as performers at the concert.
Yorkshire indie band Embrace will sing their first live rendition of the official England World Cup anthem, World At Your Feet, at the May 20 event.
Black Sabbath rocker Osbourne, 57, who sang at Buckingham Palace for the Queen's Golden Jubilee, said: "The Prince's Trust 30th Birthday will raise awareness of the problems facing over a million young people in the UK and I am proud to help make a difference," the Prince's Trust Ambassador said.
The show will also be screened live on ITV1 and presented by Cat Deeley, Ben Elton, Vernon Kay, Patrick Kielty and Kate Thornton.
The highlight of the TV event sees Ant and Dec interview the Prince of Wales, Prince William and Prince Harry together.
Fans at home will be able to watch some of the show in 3D through special glasses which go on sale from May 6.
TV viewers will be asked to pledge money to the charity, which helps disadvantaged young people in the UK, by phoning into the ITV studios.
The day after the concert an auction at David and Victoria Beckham's World Cup party will raise money for The Prince's Trust, as well as UNICEF, and David and Victoria's own children's charity. ITV1 will go behind the scenes at the star-studded fund-raising event, and broadcast the auction on May 28.
