Considered a four-star recruit by Rivals.com, Pouncey was listed as the No. 15 offensive guard in the nation in 2007. He chose Florida over offers from Florida State, Clemson, Miami, and Michigan.
Pouncey began attending the University of Florida early in 2007. His twin brother Mike would also join the Gators, playing defensive line his first season to help an injury-riddled defense. Pouncey saw action at right guard and center his freshman year. He started the season at right guard for the season opener against Western Kentucky, becoming only the seventh true freshman in team history to do so. In a week 6 loss to No. 6 LSU, he would have a grade of 86%. The next week he would have a grade of 85% while the Gators would upset the No. 8 Kentucky. On November 3, 2007, he would again get a champion grade of 83% in a win over Vanderbilt. He finished the season starting 11 games at right guard and playing in all 13. Rivals and College Football News selected him as a freshman first-team All-American and he would also be voted to the Freshman All-SEC team by the coaches and Sporting News.