But seventh-seeded Dutchman Robin Haase bucked the upset trend with a win over a plucky local wildcard, the Bangkok debutant defeating Kittiphong Wachiramanowong 6-3, 7-6 (7-1).
Top-seed Murray and number two Monfils have first-round byes on the hard courts at the Impact Arena in the Thai capital.
World number four Murray, the losing finalist to Roger Federer seven years ago, will be starting little more than a week after leading Britain to victory in the Davis Cup and has complained bitterly about the busy schedule.
Monfils will test the knee injury which kept him from Davis Cup duties as France went down to Spain in the World Group semi-final.
In opening play, Bulgarian talent Gregor Dimitrov put out number five seed Croatian Ivan Dodig 6-2, 7-5, while Thai Danai Udomchoke beat Italy's sixth-seeded Fabio Fognini 6-4, 3-6, 6-2.
Udomchoke, ranked 217th in the world, has been out for a month with a shoulder injury. And it took nearly an hour to win the first set as he played at the ATP level for only the fifth time this season.
Compatriot Wachiramanowong, ranked a lowly 523rd in the world, has yet to win any of his three Thailand Open appearances but put up a brave fight in the second set before succumbing to Haase's superior class and experience.
"When I was a break up in the second set I thought it was looking like an easy win," said Haase, ranked 42nd in the world, who won his first career title in August on clay in Kitzbuehel, Austria.
"I was playing better than in the first set. On the big points and the break points especially I was doing well. But he also played better when he was down. "I knew I didn't have to worry even if we got into a tiebreaker as I have so much more experience than him. I think that was a big advantage for me today."
Haase will next line up against 2010 losing finalist Jarkko Nieminen of Finland or wildcard Dominic Thiem of Austria.
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