William Greer was listed on the U.S. Marshals Most Wanted list for the 2006 murder of Tammy Esquivel.
Investigators said they captured Greer in a rural area of southern Mexico, where he was living with a woman and two kids.
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"It seemed like he was living pretty comfortably," said U.S. Marshals Southern District Chief Deputy Richard Hunter. "We waited for him to leave his house, go pick up his kids from school, and that's when we approached him. We didn't really give him a chance to cooperate but he didn't fight it."
Eyewitness News spoke to Esquivel's step-father, who said, "I am very happy, but I am too surprised. I don't know what to think."
Greer will be extradited back to Harris County, where he is expected to formally be charged with murder.
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