Sylvester Williams enrolled at the University of North Carolina at Chapel Hill. Williams played for the Tar Heels football team for two seasons. As a junior he had 43 tackles and 2.5 sacks. As a senior Sylvester Williams was named to the All-ACC first team as well as named an All-American by Pro Football Weekly. Sylvester Williams started all 45 games of his collegiate career at both the University of North Carolina (2011-12) and Coffeyville Community College (2009-10). Sylvester Williams was selected with the 28th overall pick in the first round of the 2013 NFL Draft by the Denver Broncos.