Jordana Brewster with Zachary Levi, Chuck

When Chuck spies an ex-girlfriend — actually, the ex-girlfriend, college sweetheart Jill — it sets in motion a reunion that throws a new wrench in the oft-derailed Chuck-Sarah romance. In this Q&A, Jordana Brewster reveals how her love for Gossip led to her three-episode arc on the NBC comedy, which kicks off Monday at 8 pm/ET. Plus: Brewster previews Fast & Furious 4 and reflects on how she almost filled Angelina Jolie's shoes.

TVGuide.com: I must say, you make as good a slow-motion entrance as Yvonne Strahovksi does.
Brewster: You know what, I totally asked for a slo-mo. I'm so glad they gave it to me!

TVGuide.com: Were you a fan of Chuck beforehand?
Brewster: I actually am a big fan of Gossip Girl [which is exec-produced by Chuck creator Josh Schwartz]. But I went on a Chuck binge and saw the whole first season on iTunes. I love the show.

TVGuide.com: Jill is a cutting-edge scientist. Is it fun playing someone so bookish?
Brewster: I love it, even though I was not at all familiar with the terms I was saying. But having to straddle the comedy world and the dramatic world, and playing a smart, sassy girl, was fun.

TVGuide.com: In your first episode, we see that Sarah is quietly jealous of Jill. Does she ever reveal to you her feelings for Chuck?
Brewster: She alludes to them, but we don't have an out-and-out talk about it. That tension between her and Chuck needs to keep building.

TVGuide.com: Did you get any scenes with Matt Bomer? Bryce is the one who busted up Chuck and Jill back in college....
Brewster: I didn't, and I was so bummed! We played boyfriend and girlfriend in Texas Chainsaw Massacre: The Beginning, so it would have been really weird.

TVGuide.com: You did, however, get to witness the most unexpected kiss in the show's short history....
Brewster: And that was on my first day, by the way. It let me see how gutsy they are and how they really, really go for it. [Laughs] They had fun with that. [One of the actors involved] is such a macho guy, you would never, ever expect to see him do something like that. And [the other cast member in the scene] is pretty much up for anything.

TVGuide.com: Did you ever get to see the Mr. & Mrs. Smith pilot you did for ABC? [A contender for the 2007-08 TV season, it never got picked up.]
Brewster: I did, I did. Working on Chuck made me realize how great that would have been because it was similar in that the writing was really good and it entailed drama and comedy and spy lingo.

TVGuide.com: But wasn't a part of you afraid you'd be compared to Angelina Jolie?
Brewster: Some sort of defense mechanism came up, so I didn't think about it. But she's so beyond stunning and larger-than-life, no one could be compared to her.

TVGuide.com: Are you still open to a series-regular TV gig, or do you like bopping between movies and guest-star stuff?
Brewster: I do like the idea of going to the studio every morning and working every single day. But in order to do that and be super-dedicated, the writing has to be there. I watch tons of television, and I do love the medium.

TVGuide.com: What do you like, outside of Gossip Girl?
Brewster: I love The Office, Chuck.... And I'm a bit obsessed with House.

TVGuide.com: Oh, are you feeling the "Huddy" romance?
Brewster: No! They can't ever do that. It's like the Chuck-Sarah thing. If it ever flourishes, you lose that tension. And the tension needs to always be there.

TVGuide.com: You, Paul Walker and Vin Diesel reunited over the summer for the fourth Fast & Furious movie. Is it faster and more furious than the original?
Brewster: It is way more fast and way more furious. It's going to be great.

TVGuide.com: Why did the three of you decide to all reunite for this one, versus the previous sequels?
Brewster: It was just a matter of timing. Paul was in the second one and it didn't make sense to have me back if Vin wasn't in it, and the third one was just a completely different thing. This one is a bit more old-school, which is very cool.