The Halo singer will make her only European festival appearance while the American rockers will also top the bill at the annual event, which takes place in both Hylands Park, Chelmsford, and Weston Park, Staffordshire, across the weekend of August 17 and 18.
Other acts confirmed to play include Stereophonics, The Script, Emeli Sande, Calvin Harris, Beady Eye, Jessie J, Rita Ora, Labrinth, Ellie Goulding, Little Mix and Jessie Ware.
Surprise: Mrs carter will headline V this year - her only UK festival appearance
'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.'
A treat: Caleb Followill of Kings of Leon performs onstage at a festival in Tennessee in 2010
Get ready! Kings of Leon, Jared Followill, Nathan Followill, Matthew Followill and Caleb Followill, will also top the bill at this year's V Festival
Tickets for this year's event go on sale at 9am on Friday, March 1.
Last year's festival! Fans baked last summer at the V Festival
The Stone Roses wowed at last year's festival
Visit www.vfestival.com for more information.