On October 31, 2006, Booker made his collegiate debut with Clemson, recording six points, seven rebounds, three blocks, and three steals as starting power forward in an exhibition game against Lithuania Academy. He was allowed 18 minutes on the court, and along with Sam Perry, led the team in rebounds. Booker made his first regular season appearance with the Tigers on November 10, 2006, in the first round of the Cox Communications Classic against Arkansas State. After starting as center, he became the first true freshman to start in that position for Clemson since Tom Wideman in 1995-96. He finished the game with 6 points, a team-high 7 rebounds, and 1 block in 19 minutes of playing time. On November 12, 2006, Booker grabbed a career-best 9 rebounds vs Old Dominion for the Cox Communications Classic title. He also contributed 10 points. On November 17, 2006, Booker scored a career-high 15 points in 20 minutes against Appalachian State. Booker recorded 11 rebounds on November 24 of the same year in a win over Charleston Southern. It was his first collegiate game with 10+ boards. On December 31, 2006, he recorded his first career double-double, with 15 points and 12 rebounds on Georgia State. James Mays, one of his teammates, when asked about Booker's accomplishments, said, "What didn't he do?" Booker helped Clemson reach 14-0, their best start in 20 years. On January 6, 2007, Booker had Georgia Tech freshman Zach Peacock ejected from the game after he hit him with an elbow. On March 19, 2007, Booker scored a career-high 21 points against Ole Miss. By the end of his freshman season, Booker averaged 10.4 points, a team-high 6.7 rebounds, and 2.2 blocks. He ranked fourth nationally among freshmen in shots blocked.
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