During his visit to Costa Rica -- the only country that has diplomatic relations with the Asian giant in Central America, where most countries align with Tawain -- the Chinese leader will meet his counterpart Laura Chinchilla, as well as lawmakers and other officials.
He and his wife Peng Liyuan, a soprano singer who has stolen the spotlight during the trip, will later travel to a rural village near the capital before attending a gala dinner hosted by Chinchilla.
The Chinese president focused on trade and energy issues in talks with Caribbean leaders.
"What I found so impressive in the president of China is that he treated the leaders of small Caribbean nations no differently to how he would treat the president of United States" or Britain's leader, Bahamas Prime Minister Perry Christie said.
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Jamaican Prime Minister Portia Simpson Miller expressed hope that "something happens, something positive, for our region" after Biden and Xi's visits.
"It's a signal to us in the Caribbean that China has been taking us seriously, they have responded to the solidarity we have express them, particularly in the one China policy."
While all of these Caribbean countries, along with Trinidad and Tobago, recognise Beijing, five other Caribbean nations have forged diplomatic relations with self-ruled Taiwan, which China considers part of its territory awaiting reunification, by force if necessary.
The two split in 1949 after a civil war.
Christie also made a pitch for increasing tourism from China, and spoke to Xi about the need for direct flights to the Bahamas and relaxing visa requirements for tourists.
Xi also met with the leaders of Suriname, Guyana, Antigua and Barbuda, Grenada and Barbados.