The Scottish band will play a one-off gig at London's Roundhouse on September 22.
They join the likes of Jack White, One Direction, Usher and Noel Gallagher's High Flying Birds, who will all be playing gigs at the venue throughout September.
The group will likely play material from their upcoming new double album, which is expected to be released this year.
They will be supported on the night by fellow Scottish band Frightened Rabbit.
Biffy Clyro's currently untitled new album was originally called The Land At the End of Our Toes and The Sand At the Core of Our Bones.
The lineup for the iTunes Festival so far is as follows:
Usher (September 1)
Ed Sheeran (2)
Olly Murs (3)
Emeli Sande (5)
Plan B (5)
Jack White (8)
Norah Jones (10)
Noel Gallagher's High Flying Birds, The Soundtrack Of Our Lives (12)
Labrinth, Josh Kumra (14)
David Guetta (15)
Rebecca Ferguson (16)
Andrea Bocelli (18)
One Direction (20)
Jessie J, Lonsdale Boys Club (21)
Biffy Clyro, Frightened Rabbit (22)