The band will play the music event on June 23, joining Bruce Springsteen and Tom Petty as the third and final headliner.
Petty will top the bill for the opening night of the festival on June 22, while Springsteen will close the event on June 24.
Pearl Jam will be preceded by performances from Biffy Clyro and Madness, while Noel Gallagher's High Flying Birds, The Vaccines, Elbow, Noah and the Whale and Example have all been booked to appear across the weekend.
The band have also announced plans to play a one-off show at Manchester's Evening News Arena on June 20.
Pearl Jam are currently working on their tenth studio album, which will serve as the follow-up to 2009's Backspacer.
The US group celebrated their 20th anniversary earlier this year by broadcasting their documentary film Pearl Jam Twenty across 67 UK cinemas.
Watch Pearl Jam perform 'Just Breathe' live below: