Matt Bomer and Eliza Dushku

Long before he made fedoras and police anklets stylish on White Collar, Matt Bomer romanced Eliza Dushku on the Fox sci-fi series Tru Calling. But when White Collar creator and executive producer Jeff Eastin came calling for her to guest-star on the USA series, Dushku knew she wanted to channel another, very famous, on-screen couple for their reunion.

"I wanted a Mr. & Mrs. Smith vibe," Dushku tells TVGuide.com. "[I said] I'd love to come and be on it, but only if it's something that's really special and only if Raquel and Neal really have a Mr. & Mrs. Smith dance going on. It could be sexual at times, it could be violent and scary at times, but as long as it's intense, and he really responded to that."

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Judging from the previews for Tuesday's episode, airing at 9/8c on USA, the message was definitely received. Neal will find sparks with Dushku's character, an Egyptologist named Raquel who has connections to his sworn enemy, Matthew Keller (Ross McCall). Thanks to his charm and bad-boy appeal, love interests come and go fairly regularly for the con man turned criminal informant, but Dushku is confident her character's connection is "a little bit deeper" compared to Neal's many other admirers.

"What was interesting to me was that she was almost the female version of him," Dushku says. "I just think it's sort of an irresistible sort of connection where they are so much alike and they are both just extremely charged and primed for each other, even if they weren't expecting it."

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Behind the scenes, Dushku says the offer to guest-star on White Collar was hard to resist. After receiving Christmas cards from Bomer for years ("I wish I could be that organized," she says with a laugh), Eastin took matters into his own hands in May when he urged White Collar fans to tweet at the actress that they wanted to see her on the show. Dushku's boyfriend bumped into Eastin soon after and she knew the timing was right.

On top of being a fan of the show, Dushku said she was excited for her and Bomer to pick up where they left off. "As actors, because we have this past and this friendship, we were really able to turn on that extra layer and level of intimacy and of real connection," she says. "During one scene where we share a little moment in my loft when we're looking around at these various items, there were a couple takes where it got hot. They called cut and Matt would run up and go, 'Did you feel that?!'"

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Bomer also surprised Dushku off-camera. "I was really impressed by Matt. I knew him when, and now he has this huge hit and he's on every single billboard and taxicab and bus in New York City and the guy is just as humble, if not more so, than he ever has been," she says. "I was a little nervous because I've seen the way that fame can start to turn people into being less than classy. That was not the case with him."

Aside from re-uniting with Bomer, Dushku says she enjoys guest-starring roles on series (such as her 2010 appearance on The Big Bang Theory) because they allow to her focus on her other job — producer. Dushku, who runs a production company with her brother, has moved behind the camera since Buffy creator Joss Whedon encouraged her and helped her become a producer on their most recent collaboration, the short-lived series Dollhouse. "These kind of guest-starring roles allow me to do both," she says.

Does that mean Dushku may return to White Collar?

"We just have to see what kind of arc they have in mind," she says. "It's definitely a pretty exciting stand-alone episode, but the door is open and we'll see what they have in mind."