After decommitting from UCLA in June 2009, Williams quickly found a home in New Mexico in March 2010, and blossomed into a reliable player for Steve Alford's Lobos squad. Williams scored a career-high 20 points in a 91–54 decision against Longwood University and posted his first collegiate double-double against Colorado, putting up 18 points and 11 assists in a 89–76 win. Williams also jockeyed for scoring leader for the Lobos, and consistently dished out the second most assists on the team (behind Dairese Gary). In addition, Williams both maintained one of the top six assist-to-turnover ratios (2.15 assists to turnovers) in the Mountain West Conference, and led the conference in three-point shooting percentage, both incredible feats for a true freshman. On March 7, 2011, Williams was selected as the Mountain West Conference Freshman of the Year after averaging 10.1 points per game and 3.7 assists per game. In his first collegiate postseason game, Williams led the Lobos in scoring with a 16-point performance against Colorado State in a 67–61 victory.