Pouncey would begin 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 rittled team. Maurkice would see action at right guard and center his freshman year. He would begin the season starting at right guard for the season opener against Western Kentucky, becoming only the seventh true freshman in school history to do so. In a week 6 loss to #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 #8 Kentucky. On November 3, 2007 he would again get a champion grade of 83% in a win over Vanderbilt. He would end the season starting 11 games at right guard and playing in all 13. Rivals and College Football News would vote him to be a Freshman first-team All-American and he would also be voted to the Freshman All-SEC team by the coaches and Sporting News.
Beginning in 2008, Pouncey would become the full-time starting center for Florida next to his twin brother Mike at right guard. He would amass 6 games with a grade of 90% or better. The first would come in week 3 against Tennessee, where he would have a grade of 93%. In week 6 he would garner SEC Offensive Lineman of the Week for his performance against Arkansas. Pouncey would have a season-high grade of 97% against LSU and then 98% the next game against Kentucky. While playing South Carolina he would have a grade of 90, his last above that mark for the season. The Gators would go on to win the SEC Championship and then defeat University to win the FedEx BCS National Championship.
In the season opener against Charleston Southern, he would begin 2009 with a grade of 98% and have 2 knockdowns in the game. The next week he would again post a grade of 98% in a victory over Troy. In the first SEC game of the year, Pouncey would play 61 snaps and receive a grade of 93% for the game. During the week 4 matchup against Kentucky, he would end with a grade of 90% and receive Champion Club Honors. On October 10, Florida would go into Death Valley to face #4 LSU. He would have a season-high grade of 99% in the 13-3 victory over the Tigers. His 28th consecutive start would also be his last game at the swamp. The Gators would go on to defeat Florida State 37-10. After going undefeated the entire regular season, the gators would lose to #2 Alabama in the SEC Championship. His last game would be the 2010 AllState Sugarbowl against #4 Cincinnati and he would finish his season with an average grade of 91.5% and 30 knockdowns. Pouncey would win the Rimington Award, becoming University of Florida's first player to do so. He would also be voted a first-team All-American by CBSsports.com, Sporting News, Football Weekly All-American, and Walter Camp.
He would finish his career with 39 starts in 41 games played. After his junior season he would enter the NFL Draft.
His rookie year, he started in all 16 games played at the center position, and was selected to the Pro Bowl. Additionally, in accordance with his exceptional play as a center during his rookie year, he received 2 votes (out of 50) for the National Football League Rookie of the Year Award. In the AFC championship game during Pouncey's rookie year, Pouncey injured his ankle during the win and was not able to play in the Super Bowl. The Steelers would go on to lose the Super Bowl to the Green Bay Packers.
Pouncey played 14 games in 2011 then 15 games in 2012. Both those years, he was a Pro Bowl selection.
In Week 1 of the 2013 season, Pouncey tore his right ACL and MCL after Steelers guard David DeCastro accidentally dove into Pouncey's right leg while trying to assist Pouncey in blocking Tennessee Titans defensive tackle Sammie Lee Hill. He was subsequently placed on injured reserve, ending his season.
On June 12, 2014, the Pittsburgh Steelers signed Pouncey to a 5-year, $44 million contract extension. This extension made him, at that time, the highest paid center in the National Football League. After a successful recovery from knee surgery, Pouncey started all 16 games in 2014 and was selected to the Pro Bowl for the fourth time of his career.