Brad and Angelina At The 81st Annual Academy Awards with ABC pre-show host Tim Gunn.

Tim Gunn still can't get over meeting Brad Pitt and Angelina Jolie while hosting ABC's Oscar pre-show on Sunday.

"That was a pure unbridled ambush!" he told Usmagazine.com Thursday at the 21st annual Bailey House auction and party in NYC. "Because if my brain had been operating more than my viscera, I never would never have had the courage to [go up to them]."

After approaching them, Gunn told Us, "they couldn't be lovelier, and what a stunning couple they are! I've never seen them up close like that! Stunning, stunning! And you can tell there's this synergy between them and there's just this incredible affection. It's very touching."
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