The US singer - famed for hits such as Crazy In Love and Single Ladies - will perform at the twin-site event in August, along with chart-toppers Kings Of Leon and double Brit-winner Emeli Sande.
Beyonce's performance will be her only European festival appearance of the year.
The event - staged at Hylands Park, Chelmsford, and Weston Park in Staffordshire - is taking place over the weekend of August 17 and 18.
CLICK ON PHOTO TO ENLARGE
The Script, Jessie J, Rita Ora and X Factor winner James Arthur will be playing V too this summer.
The Vaccines, Beady Eye, Calvin Harris and Jessie Ware are also among the first batch of stars unveiled for the Virgin Media-sponsored event.
Festival director Simon Moran said: "With our line-up already boasting acts including Beyonce, Kings Of Leon and Emeli Sande, the 18th annual V Festival is once again set to be an unmissable weekend. We have a reputation for bringing fans the best world class acts and breakthrough artists, 2013 is set to be another sensational year."
In past headliners have included Coldplay, Radiohead, Oasis and Arctic Monkeys.
Further acts are to be announced over the coming weeks.
Tickets go on sale Friday March 1 at 9am.