Williams came to Vanderbilt as one of the highest recruited players in school history. He began his career as a running back, where he led the team in rushing yards, return yards, receptions, and touchdowns, landing him on the Freshman All-SEC team. In 1998, following encouragement from Head Coach Woody Widenhofer, he switched sides of the ball to earn All-SEC honors that same year as a starting cornerback. During the 1999 season against Northern Illinois, Williams returned a punt for a touchdown in the game's final minutes for a 34-31 victory. He is one of only three players in Vanderbilt history to return both a punt and kickoff for a touchdown.