The British couple stepped out to attend The Opportunity Networks 7th Annual Night of Opportunity in New York, where they played a starring role.
Daniel and Rachel were being honoured for their contribution to the Big Apple charity, which gives talented, low-income students the opportunity to study at higher education.
Dressed in a white, sleeveless, slinky little number by Narciso Rodriguez, Rachel looked the epitome of chic. The 44-year-old actress flaunted her svelte figure and toned legs as she walked up the red carpet with her husband, and completed her look with black stiletto heels.
Rachel kept her makeup minimal and opted for slick of pink lipstick, leaving all attention to her perfectly styled brunette locks.
Daniel, 46, played up to his James Bond role as he donned a dark grey suit and pale blue shirt for the Cipriani Wall Street event. The Skyfall actor looked dapper as ever, smouldering out at the camera as he stood tall next to his wife.
Daniel and Rachel, who have been married for nearly three years, happily posed for photographers as they made their much-anticipated entrance. The couple looked more in love than ever, holding hands on the red carpet. At one point Rachel tenderly gazed up at her husband and affectionately touched his arm.
Daniel recently outlined the reasons for why he and Rachel had decided to donate year on year to the charity.
"We wanted to work with an organization that benefits the youth of the city and helps them thrive," he said. "The Opportunity Network's track record of helping low-income students create a path that leads them to successful careers is truly inspiring and something that Rachel and I are honoured to be a part of."
The Chester-born actor is set to reprise his role as Agent 007 in the James Bond franchise's next film, due for release in 2015.
Daniel and Rachel tied the knot in a private New York ceremony in June 2011. Daniel has a 22-year-old daughter Ella from his previous marriage to actress Fiona Loudon. Rachel, meanwhile, is mother to seven-year-old son Henry from her previous relationship with filmmaker Darren Aronofsky.