Maybin attended Pennsylvania State University, where he played for coach Joe Paterno's Penn State Nittany Lions football team. He redshirted during the 2006 season. He had 12 tackles, with 4.5 tackles for losses, one forced fumble and one pass breakup in 2007. He was fourth on the team with four sacks and was named to the Sporting News Freshman All-Big Ten team.

Maybin had a breakout season in 2008. He was selected as the Big Ten Defensive Player of the Week following a six-tackle, two-sack performance in Penn State's 48-7 defeat of Wisconsin, in which he also forced two key fumbles. He was named a Mid-season All-American by Sports Illustrated, College Football News and CBS Sports. At the end of the season, he was named a consensus All-American and a consensus first-team All-Big Ten selection.

Maybin was on the 2008 Walter Camp Award watchlist and was one of three finalists for the 2008 Ted Hendricks and Chuck Bednarik awards, awarded annually to collegiate football's top defensive end and defensive players, respectively. He was named the Pigskin Club of Washington, D.C. National Defensive Player of the Year.

He went on to play 4 Years in the NFL / CFL