When Brad Pitt arrived on the red carpet at Grauman's Chinese Theatre in Hollywood with his partner Angelina Jolie on August 10, she beamed with delight as she ignored him and literally hogged the spotlight. "As soon as Angelina stepped out of their car, she left Brad behind her," an onlooker tells In Touch. "She signed autographs for fans by herself and didn't seem to care where he was." It was supposed to be Brad's night. But Angelina, who arrived in a seductive strapless black leather cocktail dress by Michael Kors and four-inch stilettos, completely upstaged Brad, who accessorized his simple black suit with aviator sunglasses, which he never took off.

Brad had taken great pains to look his best for the premiere. "He wanted to look perfect," the insider reveals. "He even went to the dermatologist and dentist this month." But it looked like Angelina stole Brad's thunder intentionally, the insider adds: "She had the dress delivered that day and wore the hottest shoes from Christian Dior. She wanted to make sure that everyone knew she was sexy again." Angelina also chatted with journalists. "But Brad looked so mad he kept pulling Angie away from interviews, he seemed annoyed that she was talking so much," the onlooker adds. Angelina insulted him, to boot. When asked if she'd like to work on a movie with him again, she shot down the idea. "I would love to but we've got a lot of kids to raise," she said flatly. Brad seemed so angry with Angelina, he walked ahead of her, dragging her by the hand. After the red carpet, the two skipped the movie, and snuck out and into a private car.

For more on Brad and Angelina, pick up this week's issue of In Touch Weekly, on newsstands now.