Ed Sheeran is also on the bill for May 17 ceremony
The pair will play the Little Mix-penned track on Sunday, May 17.
The song has been produced by The Invisible Men, who helmed the Azalea hit ‘Fancy’.
It is Spears’s first major awards show performance since her appearance at the 2007 MTV Video Music Awards, where she gave a widely panned performance of ‘Gimme More’.
The singer took to the Billboard Music Awards stage with Rihanna and Nicki Minaj in 2011, but only appeared briefly at the end of each performance.
‘Pretty Girls’ is due to be released on May 5 in the US, a UK release date is yet to be set. Spears teased lyrics from the track with help from a string of emojis.
Spears recently posted a photo of dancers in a studio with the caption, “Aren’t these girls pretty?”
Ed Sheeran is also expected to perform at this year’s ceremony which will be hosted by Ludacris and Chrissy Teigen.
Spears took to Twitter to thank her crew and fans after she picked up two awards from the Las Vegas Review Journal.
The singer has been performing her ‘Piece of Me’ residency at the Planet Hollywood Casino and Hotel in Las Vegas since December 27, 2013, and has now been recognised with gongs for Best of Last Vegas and Best Bachelorette Party.