The actress stunned in a floor-length black Michael Kors gown at the 3rd Annual Save the Children Illumination Gala Tuesday in New York City.
After posing for photos, Garner, 43, stopped to give Brad Paisley and his wife Kimberly Williams-Paisley a quick hug on the red carpet and then slipped inside to host the evening for the organization, for which she is a trustee and longtime supporter.
Paisley, who took the stage later in the evening to perform three of his songs, said he got involved with Save the Children through Garner, who reached out to him after finding out they both grew up in West Virginia.
“I was roped into this by Jennifer who is from my home state – we’re both proud Mountaineers, proud West Virginians,” Paisley, 43, told PEOPLE at the gala. “We had some mutual friends and a couple of years ago she contacted me and said, ‘Hey, would you want to come see what we’re doing with Save the Children in West Virginia?’ So I said, ‘Hey, let’s go,’ and we went up and spent the day and it really runs the gamut. We went to a house and watched what they do with the families in need, we watched what they do with the school… I couldn’t believe what this organization was doing.”
Garner gave a speech introducing the organization and the evening’s honorees (who included Olivia Wilde), telling a personal story about her own visit with Save the Children to a family in need and how the charity is helping support children and families.
“I wasn’t surprised to see that the only books there had been provided by Save the Children, that there were no Crayolas, no developmental toys, no art projects creating a happy clutter like what’s in my kitchen or yours – because in poor communities, there’s one book for every 13 children in the US and I have yet to go on a home visit where children’s art is displayed on the walls,” Garner recalled, thanking the audience for being there to support “the wellbeing of children in America and the world.”
Shortly afterwards, Garner took the stage to present an award to Toms shoes with an 11-year-old boy, Hunter. The actress was all smiles as she patiently helped him read his lines from the teleprompter.
Garner and Ben Affleck, 43, who announced their split in June after 10 years of marriage, have continued to set their differences aside to co-parent their three children: Violet, 9, Seraphina, 6, and Samuel, 3.
A source tells PEOPLE in the magazine’s new issue that the two are “figuring out right now how they can best spend the holidays together,” adding that Garner “wants to get along with Ben for the kids’ sake.”
Affleck, meanwhile, has been busy working in Boston on his next film, Live By Night, which he stars in and directs.