Chesterfield arrived on the back of a 5-1 victory against Millwall last week so it was always going to be an interesting fixture.
Martin Foyle was forced to shuffle his pack after only 13 minutes when an injury to Colin Miles brought about the introduction of injury prone defender Michael Walsh.
In a closely contested first half, Chesterfield took advantage of a 23rd minute set-piece when a right-sided corner was swung in by Kevan Hurst for Aaron Downes to head unmarked into Mark Goodlad's bottom left corner.
A dubious decision by the linesman almost gifted the visitors a second in the 37th minute when Hurst fed Caleb Folan 10 yards from goal but a terrific finger tipped save forced the striker's shot over the bar.
The Valiants drew level in the 44th minute when Akpo Sodje's scuffed volley provided a perfect pass for Leon Constantine who coolly slotted past Barry Roche for his fourth goal in as many games.
The home side continued where they had left off after half time with both Constantine and Danny Sonner trying their luck from distance but good saves by Roche denied any further goals.
Chesterfield quickly got themselves back into contention when Folan missed a golden opportunity from only two yards after Paul Hall and Phil Picken had combined well to supply a ball across the face of goal.
Vale finally broke the away side's pressure in the 61st minute when a looping cross from the right by Danny Whittaker found Jeff Smith lurking at the back post but his header was misdirected over the bar.
Foyle's men pulled ahead in the 76th minute when a Sonner free kick was swung into the box and knocked into the path of the arriving George Pilkington for the captain to head home from five yards out.
Their lead was short lived, though, as when Picken crossed from the right in the 85th minute, Folan arrived with a superb header leaving Goodlad with no chance.
The match had one final twist just three minutes before the end when a rapid counter-attack by Vale resulted in Constantine stroking a placed shot into Roche's bottom left-hand corner from 20 yards.