Saudi Arabian producer Mohammed Al Turki also attended the star-studded fundraiser, along with John Legend and Chrissy Teigen, and Orlando Bloom.
German model and presenter Klum attended with her husband Tom Kaulitz and daughter, Leni Klum, 17. Klum chose a shimmering silver gown by Lebanese designer Elie Saab for the event.
Also in a gown by a Middle Eastern designer was Teigen. The model wore a feathered and sequinned Zuhair Murad number at the gala.
Czech model Karolina Kurkova, former Miss Universe Olivia Culpo, Sabrina Elba, the model wife of actor Idris Elba, and US socialite Nicky Rothschild Hilton and her British banking heir husband, James Rothschild, were also on the guest list.
Of the event, luxury retailer LuisaViaRoma writes on its website: "Unicef Italy is committed to finding new ways to support Unicef programmes through fundraising, advocacy and education in Italy. It is funded entirely by voluntary contributions from individuals, businesses, foundations and governments.
"We are committed to finding always new ways to save children’s lives, as in the case of the inaugural Unicef Summer Gala: a new opportunity to involve more and more people at our side and find valuable allies to help children."
The event was held at the Certosa di San Giacomo monastery on the Italian island of Capri. The brand LuisaViaRoma has hosted the Unicef Summer Gala since 2018.