"It's obviously an honor to be here," the humble Oscar winner said.
But look who was by Nicole's side -- none other than Brad Pitt and Angelina Jolie.
The superstar trio hit the red carpet for the premiere of "God Grew Tired of Us," an emotional documentary about three men overcoming hardship in Africa and then meeting more adversity when they start over in the U.S.
"The men whose stories this film tells is what's so compelling," Nicole admitted.
On Monday night, John Dau and the other men who star in the film met the stars for the first time.
"They said we got your back, and we can help you," Dau related.
Nicole, who narrates the film, said the men are a true inspiration.
"There's no bitterness, and they've encountered some incredible trauma and devastation in their lives," she said. "And yet they shine."
"It's also a reminder that there are 20 million refugees around the world, and the situation in Darfur is getting worse every day," Angelina added.
Angelina, whom we spotted sharing a tender touch with Brad, said her critical comments about Madonna's African adoption were misconstrued, and that she fully supports the Material Girl.
Brad also confirmed the reports about adding to their ever-growing family.
"Of course," Pitt said when asked if adopting more kids is a topic he and Angie discuss.
The sexy superstar also revealed to "Extra" why he executive produced the film.
"It makes me think of my kids and the future that they're going to have," he said. "And I think about the lives they could've had."
While Brad and Angelina had each other for the big night, Nicole arrived solo on the red carpet.
But she was glowing as she made her first public appearance since her husband, country superstar Keith Urban, entered alcohol rehab.
"I always get shy and embarrassed when someone says that," Nicole said when complimented on her transcending beauty. "I've got to learn to take a compliment better, I'm told."