Gen Prayut and Foreign Minister Don Pramudwinai were on hand at Government House to welcome the Chinese leader when he arrived at about 1.25pm.
A welcoming ceremony was held at the Thai Khufah Building.
The two leaders took part in full bilateral talks involving government ministers from both countries.
Following the talks, Prayut hosted a lunch for the Chinese leader, who is on an official visit to Thailand.
Xi arrived at Government House in the China-made Hongqi luxury car that he had also used during the summit, shunning the BMW i7 electric sedans that Thailand had prepared for Apec leaders.
Hongqi, which means “red flag” in Chinese, was launched in 1959 and is China’s oldest car maker.
The Thai prime minister met with Xi just after completing his task of hosting the summit of 21 member economies of the Asia-Pacific Economic Cooperation at the Queen Sirikit National Convention Centre in Bangkok.
During the closing ceremony, Prayut handed over the Apec chair to Vice President Kamala Harris of the United States, which will host next year’s Apec Summit in San Francisco.