The festival will be held at its new home Strathallan Castle for the very first time this year, reported Digital Spy.
The band last played the festival in 2004, before splitting up and reuniting last summer.
Festival Director Geoff Ellis said: "The Libertines are a truly iconic British band, revered as cult heroes by a generation of music fans and adored by the Scottish crowd. They chose Scotland as the destination for their live return on home soil last June, and raised the roof of the Barrowlands with two exhilarating shows.