The 41-year-old singer and 40-year-old actress attended the Children's Hospital Los Angeles gala at Barker Hangar in Santa Monica, Calif.
Timberlake and Biel were all smiles on the red carpet. Biel wore a black dress by Giambattista Valli with bow and feather details, while Timberlake sported a black tuxedo.
The couple posed with actor Chris Pine and his father, Robert Pine, who co-hosted the event, along with a couple young patients.
Timberlake and Biel were also joined by Biel's brother, Justin Biel, whose daughter had life-saving surgery at Children's Hospital Los Angeles.
"So special having my brother with us - his daughter had a life saving heart surgery at CHLA and we are so grateful and proud to be part of this community. Shout out to little Zamboni! Thanks you everyone who came out @childrensla," Biel wrote on Instagram.
The gala helped raise $5.5 million for pediatric medical care and research initiatives at Children's Hospital Los Angeles.
Timberlake performed a medley of his biggest hits with a 4-year-old patient, Ella.
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Timberlake and Biel married in October 2012 and have two children, sons Silas, 7, and Phineas, 2.
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