Williams held the third-base job before leaving to become the Washington Nationals manager in 2014. He was fired by the Nationals last month after posting a 179-145 record in two seasons.
From 2010 to 2013, Williams was the Diamondbacks' first-base coach and then moved to third on former manager Kirk Gibson's staff. Williams will now be part of manager Chip Hale's coaching staff.
Williams played third base for the San Francisco Giants, Cleveland Indians and Diamondbacks during his major league career. The five-time All-Star and four-time Gold Glove winner hit 378 home runs and drove in 1,218 runs. He shares a club record of 142 RBIs in a season.