The news comes just days after Rihanna made a series of changes to her ‘Anti’ world tour, altering the start date, and cancelling two concerts which were due to take place in Sunderland and Cardiff.
Nevertheless, the ‘Work’ star is now set to perform at the festival, which takes place across two locations, on 20 and 21 August.
Rihanna and Biebs are joined on the line-up by a number of other big names, including Sia, Little Mix, Rita Ora and Craig David.
All Saints, Fleur East, Example, Katy B and Jess Glynne are also along the stars who'll be performing.
Rihanna is yet to begin promoting her most-recent release ‘Anti’, and last week, she cancelled on the Grammys, just hours before she was due to perform.
The ‘We Found Love’ singer is set to appear at the Brit Awards on Wednesday (24 February).
See the full V Festival line-up, and find out how to get tickets, here.