The League Two visitors won it 1-0 thanks to a long-range strike from James Wilson.
But overall Chesterfield can be encouraged by their performance against a side who start their season this weekend.
Vale stopper Lucas Covolan was sent off late on for an apparent elbow on Nathan Tyson as the game threatened to boil over towards the end.
Here are some pictures from the game taken by DT photographer Jason Chadwick...
Vale stopper Lucas Covolan was sent off late on for an apparent elbow on Nathan Tyson as the game threatened to boil over towards the end.