The dual festival will take place at Hylands Park, Chelmsford and Weston Park, Staffordshire over the weekend of 17th and 18th August.
Emeli Sande, Calvin Harris, Jessie J and Olly Murs will also perform at the 18th staging of the festival, organisers said.
The line-up will also feature: Stereophonics, The Script, Calvin Harris, Beady Eye, Two Door Cinema Club, The Vaccines, Basement Jaxx, Paloma Faith, James, Rita Ora, The Courteeners, Jason Mraz, FUN., Labrinth, Ellie Goulding, Kendrick Lamar, Of Monsters And Men, Maverick Sabre, Travis, DJ Fresh/LIVE, Jessie Ware, Maximo Park, Lianne La Havas, Rudimental, James Arthur, Scouting For Girls, Deacon Blue, Little Mix, Ocean Colour Scene, The Fratellis, Gabrielle Aplin and Laura Mvula.
Tickets for V Festival go on sale on 1st March at 9am.
Festival Directors Bob Angus, Simon Moran and Dennis Desmond sad: "We've worked hard to bring fans an exciting and diverse line-up, securing Beyonce for an exclusive European Festival appearance and Kings of Leon as headliners is a great achievement.
"These acts along with one of the strongest bills in V Festival's 18 year history is something we are very proud of. We have a reputation for bringing fans the best world class acts and breakthrough artists, 2013 is set to be another sensational year.”