The Wizards announced Wednesday that Jamison will be the team's new director of pro personnel. Jamison, 43, has been a scout for the Los Angeles Lakers the past two seasons.
The Wizards also announced the hiring of Laron Profit and John Carideo as scouts.
Jamison played 5½ seasons with the Wizards, beginning in 2004-05; he was traded to the Cleveland Cavaliers in a three-team deal in February 2010. In 421 games with Washington, he averaged 20.8 points and 8.9 rebounds. He played in the 2005 and 2008 All-Star Games.
"We are absolutely thrilled to bring Antawn back to the Wizards organization," general manager Tommy Sheppard said in a statement. "In addition to his strong feel for the game and basketball knowledge, he has always been a true professional and a dedicated worker. We look forward to him bringing those qualities to our front office."
The Wizards have retooled their front office since firing longtime GM Ernie Grunfeld in April. In addition to naming Sheppard the new GM, they brought in former NFL executive Sashi Brown and former Georgetown coach John Thompson III.
Jamison had a 16-season playing career that ended in 2014. He was selected No. 4 overall by the Raptors in the 1998 draft but was traded to the Golden State Warriors in a draft-night swap that sent his North Carolina teammate Vince Carter to Toronto.