Williamson, who made 62 appearances for the Spireites during a two-year spell in the 1980s, will also be involved in coaching the new development squad which is being introduced.
Former Chesterfield player Charlie Williamson has today been named as the club's new head of recruitment/chief scout.
Commenting on his appointment, Williamson said: "I can't tell you how excited I am to be back involved again. It's a great opportunity for me and I'm really looking forward to it.
"The brief is to look at teams we're coming up against and also look out for players who can make the squad as strong as possible. The more information we can get on players, the better it is going to be."
The 57-year-old will draw on his youth development experience with Sheffield Wednesday to help the youngsters in the development squad. He said: "I've always had a major interest in developing players. The manager is looking at 18/19-year-olds being involved in the development group and the plan is to play games on a weekly basis."
Manager John Sheridan added: "Charlie is very experienced in football and I think it's important to have someone going out and hopefully finding players for us.
"He'll be out and about, watching players and be involved with the development squad as well. Charlie has got some good contacts in the game and I'm very confident that he'll be a great asset."
Williamson began his career at Sheffield Wednesday and had spells on loan at Lincoln City and Southend United before joining the Spireites in 1985.