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The 64-year-old royal, who is married to former Olympian swimmer Princess Charlene, 44, donned a dapper navy blazer and grey trousers for his solo appearance in Monaco.
The mother-of-two, 44, could be seen bowing her head as she walked through the San Damaso courtyard with her husband Prince Albert, 64, following the meeting.
In photos shared on Prince's Palace Instagram page, Princess Charlene of Monaco, 44, could be seen in a white top and bold red lipstick as she posed with her family.
This evening's social and charity event was launched in 1948, when Prince Rainier III of Monaco presided at the first gala held by the newly founded Monaco Red Cross.
Princess Charlene of Monaco, 44, posed for pictures at the Palace with her husband Prince Albert of Monaco, 64 as the pair welcomed guests. She wore a sleek back outfit and a silver necklace.