The 33-year-old, who turned down a move to Football League newcomers Burton, has signed a two-year deal at Saltergate and becomes John Sheridan's first signing since he was installed as manager last month.
Former Spireites captain Breckin made 249 appearances for the club between 1997 and 2002.
He said: "I am delighted to be returning to Chesterfield at a time of historic change for the club with the move to the new stadium."
Manager Sheridan added: "I am really pleased to sign a player with
great experience who has a hunger to help us get out of League Two.
"We have done well to get him as a number of other clubs were competing for his signature."