Williams attended Dekaney High School in Spring, Texas, a suburb of north Houston, where he was a three-year letterer and starting tailback for the Dekaney football team. As a sophomore, he rushed for 1,930 yards, 18 touchdowns, and was named District 13-5A Newcomer of the Year. As a junior, he had 251 carries for 2,290 yards and 20 touchdowns, receiving District 13-5A MVP and Class 5A second-team All-State honors.
As a senior, he had 447 carries for 3,890 yards, 48 touchdowns, 10 kickoff returns for 346 yards and 2 touchdowns, to go along with 6 punt returns for 113 yards and one touchdown. He helped lead Dekaney High School to its first ever state championship game, where the Wildcats beat previously undefeated Cibolo Steele High School 34–14 to win the championship. Dekaney was ranked the 23rd best team in the nation by Maxpreps, and Williams himself was listed as a 5-star recruit by 247sports. He was ranked as the 2nd best running back in the nation, the 4th best player in Texas, and the 18th overall best athlete in the nation. ESPN also called Williams the "fastest player in high school football". Trey Williams finished his high school career with 8,110 yards rushing yards (8.7-yard avg.) and 86 touchdowns. He accepted an offer from Texas A&M over offers from Alabama, Arkansas, Auburn, Baylor, Florida, Louisville, LSU, Notre Dame, Oklahoma, Oklahoma State, Oregon, Texas, and several other colleges.
Trey Williams additionally played baseball and had a .383 batting average. He also ran track and was named all-state all four years of high school.

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