Giovanni Rufino / The CW
Here she is! Hilary Duff joins the cast of Gossip Girl as movie star Olivia Burke for the Oct. 5 episode titled "Dan de Fleurette," and we have the exclusive first look at Duff in character on the set!
Duff's character is assigned to be Vanessa's (Jessica Szohr) roommate at NYU—their dorm room is the setting of the still above—and through Vanessa, Olivia gets to know Dan Humphrey (Penn Badgley). Olivia becomes attracted to Dan, and vica versa. Of course, there's a twist: Dan is so tuned out to pop culture that he doesn't realize the girl he's falling for is a huge movie star famous for her role in a Twilight-esque series of vampire movies.
Still, the two college kids manage to make their odd-couple pairing work, and cuteness ensues. Yay!