The former Verve frontman - who released single 'Black Lines' last year - will make a comeback supporting the Pink Floyd legend at the London landmark on July 6, along with the 'Up The Junction' hitmakers and unique guitarist.
James King, Senior Vice President of AEG Presents, said: ''Roger Waters consistently delivers the most exciting live experience I've ever seen.
''To see his live show on The Great Oak Stage providing a soundtrack of Pink Floyd's greatest hits will be a spectacle not to be missed.''
It follows the announcement that Paul Simon will make his final UK appearance at the music extravaganza.
The 76-year-old musician confirmed he is to bring the curtain down on his performing career by headlining on July 15.
Simon will be joined by James Taylor and other guests for the much-anticipated show, which King has already described as an ''unmissable event''.
He said: ''Paul, James and Bonnie all together on the Great Oak Stage has to be the show of the summer and a truly unmissable event.''
Tickets for Simon's UK finale are already available through Barclaycard pre-sale, and are due to go on general sale at 9am on Tuesday, February 2.
Other headliners this year are Eric Clapton, Michael Buble, Bruno Mars and The Cure.
Last year's BST festival was headlined by Green Day, Justin Bieber, The Killers, Phil Collins, Kings of Leon and Tom Petty, who sadly passed away in October at the age of 66.
The event first launched in 2013 with The Rolling Stones being that year's standout headliners, and has since featured top of the bill performances from the likes of Stevie Wonder, Neil Young, Florence + The Machine, Taylor Swift, Take That and The Who.
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