Jordana Brewster has signed on for a multi-episode arc on "Chuck," playing a pivotal figure from the main character's past.

Series executive producer and co-creator Josh Schwartz confirms that Brewster will appear in at least three episodes of NBC's "Chuck."

Brewster will play Jill, the college flame who ditched Chuck (Zachary Levi), slept with his best friend (Matthew Bomer's Bryce Larkin) and was a central part of the life spiral that left Chuck as a directionless member of the Nerd Herd when the series began.

That, of course, was before Bryce uploaded a super-computer of information into Chuck's brain, making him a key intelligence asset for several government agencies, a bumbling and unlikely spy.

When Jill reenters his life, it produces a clash of Chuck's old life and his new life and it seems likely that sparks will fly.

"This part is the reason we couldn't wait for the strike to be over and get back to work," Schwartz says. "You will get an opportunity to see Chuck back in college with Jill and how it all went down. Jordana was our first choice for the part -- someone you believe as beautiful enough to break Chuck's heart, and brilliant enough to be even smarter than he is..."

While Chuck has had ongoing romantic tension with handler Sarah (Yvonne Strahovski), the character's only other Season One love interest was Lou, a sandwich genius played by Schwartz favorite Rachel Bilson.

Expect Brewster's first appearance in the season's sixth episode, perfectly timed for the November sweeps period.

While Brewster is best known for features including "The Faculty" and "The Fast and the Furious," the "As the World Turns" veteran was one of the hot names in the 2007 development seasons. After flirting with a number of profiles, Brewster took the Angelina Jolie role in ABC's small screen adaptation of "Mr. & Mrs. Smith." That pilot obviously failed to go to series, but perhaps Brewster will now have an opportunity to show her action-comedy chops.

Other previously announced guests on the upcoming season of "Chuck" include Nicole Richie and Tony Hale.