"It was the greatest day of my life," Alec Baldwin told PEOPLE Wednesday at the Robert F. Kennedy Bridge Dedication Gala in New York.
The two locked lips during last week's episode of 30 Rock, where Aniston played a crazy friend of Tina Fey's from Chicago.
Baldwin said kissing scenes as a rule tend not to be that good. "Whenever you do that with someone, it's so fake. They're getting paid to kiss you and I'm getting paid to kiss her. But she's a doll," he said.
Baldwin, who plays GE exec Jack Donaghy on the Emmy-winning NBC show, said he appreciated Aniston making time for the appearance.
An Active Aniston"Jennifer is obviously someone who has a lot of things she could be doing with her time," Baldwin said. "Jennifer Aniston could be making films, she could be shopping, she could be buying a private island somewhere – she could be doing virtually anything she wants to do. And for her to take time to come be with us, I'm very, very grateful."
Next up for Baldwin's onscreen love life is Salma Hayek, who plays his character's girlfriend for five episodes.
"She was literally the most fabulous woman I've ever worked with," Baldwin said about Hayek. "We're all going to miss her. No one wants her to leave!"
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1995: Jen turns the world on with her shag haircut and Friends