The team announced Jamison's hiring Wednesday.
"We are absolutely thrilled to bring Antawn back to the Wizards organization," general manager Tommy Sheppard said. "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."
Per the Wizards' announcement, Jamison will work alongside Johnny Rogers, vice president of pro personnel, scouting for the NBA, G League and international players.
Jamison had a successful 16-year NBA career with six teams from 1998-2014. He was originally drafted No. 4 overall out of North Carolina by the Toronto Raptors, who sent him to the Golden State Warriors for his college teammate Vince Carter.
From 2004-10, Jamison appeared in 421 games for the Wizards after being acquired in a trade with the Dallas Mavericks. He was named to the NBA All-Star team in 2004-05 and 2007-08.
Washington has rebuilt its front office this summer, starting with promoting Sheppard as full-time general manager. Jamison joins the franchise as it tries to rebound following a disappointing 32-50 record last season.