When Buffy the Vampire Slayer wrapped last May, Emma Caulfield was eager to shed her persona as Anya, the self-centered ex-vengeance demon. She wanted to try something different. Instead, she ended up reconnecting with her former 90210 beau, Jason Priestly. They happily reunited to make the ABC Family romantic comedy I Want to Marry Ryan Banks (Sunday at 8 pm/ET).

"I love that man so much," Caulfield tells TV Guide Online. "He is just one of those people I am so grateful that I met. He is really just one of the good ones.

"It was like no time had gone by whatsoever," she continues. "We just picked up right where we left off. And we just had such a good time. He's just lovely and I always wanted to work with him again. We had really good chemistry on Hills. How great that is, because it is rare that you have proven chemistry with someone."

In Ryan Banks, Caulfield plays Charlie, who competes on a reality show to date a famous actor played by Priestly. In a twist, she falls for Banks' best friend and manager, Todd, who's portrayed by former Alias hottie Bradley Cooper. Off screen, Caulfield had to compete for the attention of her handsome costars.

"[Cooper] is really talented, and so funny. He and Jason just got along like childhood friends," she recalls. "They just immediately clicked. They had a total little man-crush on each other. But the two of them just made me laugh, and the three of us spent a lot of time together."

Sounds like Caulfield isn't missing Anya too much. However, she was pleased with the way she ended her Buffy run. "I liked her dying," she admits. "I thought that was very poetic. To sacrifice herself for somebody else was so her whole point. [She went from] being so totally selfish and self-focused to giving the ultimate sacrifice of her life, which was just a beautiful bookend [to her story]."