As part of the association, Chesterfield's youth team will use the facilities at Staveley's Inkersall Road ground and stage certain fixtures at the venue.
Chesterfield youth-team coach Mark Smith is also keen to see some of the club's youngsters play for Staveley in order to aid their development.
"The link-up will provide a pathway for youngsters who sometimes need to compete in a senior league in order to further their footballing education," said Smith.
"Staveley manager Neil Cluxton works with our scholars as a tutor at Chesterfield College so he knows them, which is also beneficial."
Staveley chairman Terry Damms said: "We're delighted to be involved with Chesterfield's youth set-up. We are signing a 25-year lease for our junior teams on their own pitches at Inkersall Road, which illustrates our commitment to grassroots football.
"This development further strengthens our great relationship with the Spireites. We offer Chesterfield season ticket holders free admission to our home games and it's always good to see them at Inkersall Road."