Paloma Faith, Mick Hucknall and '70s favourites Average White Band will also perform at the special concert on Sunday, September 9.
Jeff Smith, head of music at Radio 2 and 6 Music, commented: "Music is at the heart of Radio 2's output, and with more incredible artists to be announced in the coming weeks, there will be something for everyone at this year's Radio 2 Live in Hyde Park.
"What better way to end the summer than with a truly British celebration of music."
Radio 2 listeners will be able to catch highlights of the concert in the following week, while the station's official website will feature exclusive backstage footage and interviews.
Last year's Hyde Park event, dubbed 'a festival in a day', saw performances from the likes of Gary Barlow, Lenny Kravitz, James Blunt and Beverley Knight.
Tickets for the 2012 concert are on sale for £35 plus booking fee. Details of how to apply can be found on the Radio 2 website.