Caroline Flack, who briefly dated the hitmaker a year ago, was a guest on British show Don't Sweat The Small Stuff when she took part in a challenge to hurl a bottle of pee at a cardboard cut-out of a celebrity's face.
Her choices were her ex and fellow British singers Olly Murs and James Arthur, who she has also been romantically linked to - and she didn't hesitate in taking aim at Styles.
Giggling with glee, the 33-year-old Tv personality launched the bottles at the pop stars.
The mask of The X Factor winner James, who has confessed to a crush on Flack, also got splashed with urine - but he loved the Tv moment, tweeting, "Thanks for throwing p**s at my head @carolineflack1 it's okay I still love ya (sic)."
Ironically, the new show is hosted by one of Styles' closest celebrity friends, Nick Grimshaw.