A double from Wayne Allison was enough to sink the visitors and give Chesterfield their fifth straight home win.
Allison would have had a hat-trick but for the marvellous reactions of goalkeeper Mark Goodlad who was one of the few plus points for disappointing Vale.
Martin Foyle's team was in some ways thrown together following the departure of Sam Collins and Billy Paynter to Hull, but they should still have put up a better display.
Chesterfield were better and sharper all over the field and although Vale created some openings, they did n0t deserve to end that poor run at Saltergate.
The Spireites always looked capable of scoring and their opener was a well-worked move in the 31st minute.
Paul Hall and Derek Niven exchanged passes on the Vale left before Hall whipped in a cross that Allison met with a right-foot drive that Goodlad saved, only for the veteran striker to bundle in the rebound.
Vale might have found a way back if Leon Constantine had done better in the 42nd minute when a mistake left him clear on goal, but he put a weak shot too close to Barry Roche who kept the ball out with his legs.
Vale should more urgency in the second half but they still could not finish off some promising moves.
Poor control from Mark Innes denied him a great opening in the 52nd minute and then Constantine dragged another effort wide.
Innes looked certain to score against his former club in the 64th minute after Constantine put him in, but Roche made another vital save to his right.
That was a big moment in the game as Chesterfield broke away two minutes later to score again.
Colin Larkin drove a fierce shot against the crossbar and the rebound fell to Allison who tucked away the chance from six yards.
That was game over, although Allison was denied a hat-trick by a great save from Goodlad six minutes from the end.