Jones was named the Vice President of Basketball Operations.
"James has a wealth of experiences that will greatly benefit our organization", McDonough said in the release. He's a three-time National Basketball Association champion, winning two in Miami and one in Cleveland.
Jones had joined James in the past seven NBA Finals, and retires with three championship rings.
McDonough is entering his fifth season as general manager and is the architect of an exceedingly young roster built with draft picks. "We have laid the foundation for what we hope will become the next championship-caliber Suns team".
Jones was a part of all four Finals teams in Miami from 2011-2014, and then thanks to his friendship with LeBron James, made his way to Cleveland and played in all three of the Cavaliers' Finals matchups against the Warriors. He averaged a career-high 9.3 points per game in 2005-06.
'Nepotism rocks' barb: Kangana Ranaut affected by joke?
If they had given more thought to it, they could have finished the long ongoing public discourse on nepotism more decisively. Talks on the issue got a fresh boost after the "Nepotism rocks" act at the recently held IIFA Awards.
Jones rarely played and was never a consistent member of the rotation, but his fellow players, along with Cleveland coach Tyronn Lue and his staff, loved the 36-year-old's wisdom and knowledge of the game, as well as the professional way in which he always approached it.
The Suns went 24-58 last season, the NBA's second-worst record and worst in the Western Conference.
Formerly the Secretary-Treasurer for the National Basketball Players Association, Jones comes to the Suns after most recently appearing in 48 regular-season and eight playoff games for the Eastern Conference Champion Cleveland Cavaliers in 2016-17.
In addition to the Heat, Jones played for the Pacers, Suns, Trail Blazers and Cavaliers. He and his wife, Destiny, have three children.