The 'Can't Go Back' band will be joined by 'Price Tag' singer Jessie J and 'Pack Up' performer Eliza Doolittle at the Orange RockCorps show, held on July 12 at Wembley Arena.
The event will see some 11,000 volunteers make up the crowd after qualifying for tickets by giving four hours of their time to one of the Communication company Orange's community projects.
Eliza ' who played at the venue last Wednesday (11.05.11) for the National Movie Awards ' cannot wait to take to the stage again.
She exclusively told BANG Showbiz: "Playing at Wembley is always a special event, especially as it's such a good cause.
"I can't wait to come and play here for the volunteers on July 12."
Non-profit organisation RockCorps have previously put on concerts with Lady Gaga, Snoop Dogg, N-Dubz and Korn for their volunteers ' and Stephen Greene, CEO and co-founder of the company, is delighted with this year's line-up.
He said: "I'm pretty stoked. To get a band the size of Primal Scream to come out and inspire all our volunteers is incredible.
"Primal Scream is like one of these great iconic acts, it takes a little bit to line everything up. But when they, like Jessie J, heard they could come play the show and inspire 11,000 volunteers they made sure they could do it.
"Eliza's fantastic, it was a really easy ask. We told her what we were doing and she said: 'When do you need me? I'll be there'."
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