Thompson's selection to succeed Joanne Boyle, who led the Cavaliers to this year's NCAA tournament, is a splashy and out-of-the-box first coaching hire for new Virginia athletics director Carla Williams.
Thompson has spent the last three seasons as an assistant on the Texas staff, but is no stranger to the spotlight.
She won four WNBA championships and two Olympic gold medals.
Thompson was inducted was voted into the Women's Basketball Hall of Fame and the Naismith Memorial Basketball Hall of Fame.
It will be the first head-coaching job for Thompson, 43. This program is in an exciting place with a hardworking group of young ladies. "When I told him the great news he said, 'Wait". As a coach, she has proven to be a tremendous teacher and recruiter.
Thompson said she was excited to work with the team to build upon retired coach Joanne Boyle's success.
The Cavaliers went 19-14 this past season and advanced to the second round of the NCAA tournament in their first appearance since 2010.
Thompson is the fifth head coach in UVa's 44-year history, including hall-of-famer Debbie Ryan, whose 34-year run included 20 straight NCAA appearances from 1983-2003.
What Thompson lacks in coaching experience - she's never coached anywhere other than Texas - she more than makes up for it with a résumé rivaling any player in her sport. I mean wow, Isn't that a good program? Correction, great program. I am so happy for you. We will do great things there!' My response to him was that I could not agree more. The Cavaliers were 19-14 overall, 10-6 in the ACC, and fell to SC in the NCAA tournament's second round. I am excited about meeting my team, getting to know them and pouring into them.
"I want to thank Carla Williams for this coveted opportunity", Thompson said in the statement.
Thompson arrived at Texas after a trailblazing career in the WNBA, in which she began as the first overall draft pick in 1997 and ended as the league's all-time leading scorer in 2013.
Throughout her 17-year professional playing career, Thompson was a four-time WNBA champion with the Houston Comets (1997, 1998, 1999, 2000), a member of the WNBA All-Decade team, an eight-time All-WNBA team selection, a nine-time WNBA All-Star and the WNBA All-Star MVP in 2000.
On the global level, Thompson has won two Olympic Gold Medals as a member of Team USA in 2004 (Athens) and 2008 (Beijing). She was the WNBA's career scoring leader until she was passed by Diana Taurasi last summer.
In September, Thompson is scheduled to be enshrined in the Naismith Memorial Basketball Hall of Fame in Springfield, Massachusetts.