The singer will play a headline set at London's Roundhouse on September 13 as part of the music service's month-long series of free-ticketed gigs.
Pink joins a lineup that already boasts sets from Usher, One Direction, Plan B, Rebecca Ferguson and Olly Murs.
Fans can apply for tickets via the official iTunes Festival 2012 website or the accompanying iOS app.
The show precedes the release of Pink's sixth studio album The Truth About Love on September 17.
The new collection features the star's new single 'Blow Me (One Last Kiss)' and a collaboration with Lily Allen.
Listen to Pink's new single 'Blow Me (One Last Kiss)' below: