The songstress, 28, joined the the 32-year-old Prince to celebrate the 50th anniversary of Barbados' independence from Great Britain, reported BBC.
Rihanna greeted the prince, who said: "Hello, it's very nice to meet you."
The singer wore a blue dress for the event and opted for striking yellow finger nails - both colours are on the Barbados flag.
Prince Harry read a message from the Queen to mark the anniversary of the moment, on 30 November 1966, that the country broke away from British rule.
"The extraordinary talents of your people, from the cricket field to the music industry have been admired and recognised throughout the world. Barbados remains a favoured holiday destination for British people, not only for the incredible natural beauty of your country but because you have a great warmth and generosity of spirit...," the message read.
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