The quartet, who last reunited in 2010 to perform at Reading/Leeds Festival, will top the bill at one of the days of the British Summer Time event in July.
The band split in 2004 after releasing just two albums with co-frontmen Doherty and Carl Barat going on to pursue their own careers.
Doherty released solo material but became better known for his drug problems, brushes with the law and relationship with Kate Moss than his music, while Barat fronted the band Dirty Pretty Things.
The Libertines will play the Hyde Park event - formally called Barclaycard Presents British Summer Time - on July 5, on a bill which also includes the Pogues and Spiritualized.
The reunion will not come as a complete surprise to fans of the band as Doherty let slip a show was on the cards in a recent interview, and the band's Facebook page featured an image of Hyde Park.
The group scored top 40 hits with singles Time For Heroes and Don't Look Back Into The Song, and their biggest hit Can't Stand Me Now, which echoed the difficulties between the once-loyal friends Barat and Doherty reached number two. Their second, self-titled album topped the charts in 2004.
Also performing in Hyde Park this summer will be Neil Young, McBusted and Black Sabbath.
Tickets go on sale generally a week today at www.bst-hydepark.com, although some pre-sale tickets will be available earlier in the week.