Hilary Duff is set to join the CW's hit show Gossip Girl for a multi-episode arc, according to EW. Hils' will play Olivia Burke, a movie star who enrolls at NYU in search of a traditional college experience. She ends up rooming with Vanessa [Jessica Szohr]. Hilary will debut in Season 3's fourth episode, airing on October 5. Gossip Girl producers approached Hils' after NBC passed on her comedy pilot Barely Legal.