The announcement follows Andrea McCauley’s decision to step down from the role last month, after more than five seasons at the helm of the women’s program.
Williams has spent the last two seasons in an assistant coaching role with the Strikers women and following Shelley Nitschke’s departure in 2018, also took on assistant coaching duties with the Scorpions.
Contracted by both South Australia and Tasmania during the early 2000s, Williams played five first-class matches as a top-order batsman.
An Adelaide Cricket Club life member, Williams is second on the club’s leaderboard for all-time runs with 6984, including a high score of 253 not out.
He is one of just four players to win the Bradman Medal three times (2005-06, 2007-08 and 2009-10), as the best West End Premier Cricket player of the season.
Williams has been Head Coach of both the Under 15 and Under 17 State male sides in his previous position as SACA Talent Coordinator and has most recently been involved in State talent identification for female underage programs.
SACA High Performance General Manager Tim Nielsen said: “I am thrilled to see Luke appointed Head Coach of the Scorpions.
“There was an excellent field of applicants and Luke’s preparation and passion for the role and the players was palpable.
“I’m certain he will step up into this role seamlessly and will have great success moving forward.”
Williams is looking forward to the challenge of stepping into the top job.
“I’m super excited and really proud and honoured to be given this opportunity,” Williams said.
“I’ve loved my involvement with the Scorpions in recent times so I’m really excited about what the future might hold.”