All eyes were on sexy, single Jennifer Aniston as she walked into the Park Hyatt’s Roof Lounge in Toronto, but only one man caught her attention — rugged Scottish actor Gerard Butler. “They immediately made eye contact,” a witness at the Toronto International Film Festival after-party on September 7 recalls. “They had instant chemistry.” Another onlooker adds that it looked as if the pair had met before and were happy to see each other again: “It didn’t take Gerard and Jen long to gravitate to one another. When they came together, it was all hugs and smiles.”

According to partygoers, the actress, who was in town to promote her upcoming movie Management, happily flirted, chatted and laughed all night with Gerard, the star of 300 and Guy Ritchie’s latest gangster flick, RocknRolla. “She was playing with her hair and acting coy,” says the witness. “At one point, Gerard had his hand on her thigh and was whispering in her ear.”

At the end of the evening, as they were getting ready to leave, Gerard rubbed Jen’s shoulders and gave her a kiss on the head. “They looked so comfortable together,” the witness adds.