Tommy Wright, who was with the club between 1998 and 2000,Â has been charged byÂ City of London Police.
Wright, who scored one goal in 28 appearances for Rovers, has beenÂ charged with two counts of accepting a bribe.
Two other men, football agent Dax Price and Giuseppe Pagliara, have been charged with two counts of paying and facilitating a bribe.
The trio are to appear before Westminster Magistrates on 24 September.
City of London Police said the men had been charged on suspicion of bribing individuals at Barnsley Football Club.
The charges come as a result of an investigation by The Telegraph into football agents who were thought to be facilitating bribes with individuals at football clubs between May and September 2016.
Wright was sacked by Barnsley in September 2016 and after a spell at Oldham returned to Chesterfield in September 2017 to work as a first team coach for then-manager Jack Lester. He was previously assistant manager and caretaker boss of the Spireites. Â