Rotherham almost took the lead after only five minutes when a one-two between Shaun Barker and Lee Williamson allowed the midfielder into the box.
However, his low curled shot from eight yards managed to beat Mark Goodlad but not his right post.
The Valiants struck a massive blow seconds before half-time when Nathan Lowndes picked up a Michael Cummins pass 25 yards out and struck a looping shot that sailed into Neil Cutlers top right corner.
Rotherham escaped embarrassment ten minutes into the second half when a Craig James free-kick wasn't cleared, bouncing through the defence and luckily for Cutler, crashed back off the crossbar.
The woodwork was involved yet again three minutes later when John Mullin's cross from the right of the box was met by a thumping Deon Burton header.
To add to the drama, a storming run by David Worrell was ended abruptly on 61 minutes when on- loan Chris Cornes sent him tumbling in the Vale box.
Burton bravely stepped up for the spot-kick but the pressure proved too much for the striker with his weak shot being saved superbly by Goodlad low to his left.
In a game of dubious decisions, Barker was the referee's next victim when his tackle on Billy Paynter while running towards goal was judged to be a sending-off offence.
Not even Rotherham manager Mick Harford could escape the referee's wrath when he was sent to the stands in the 85th minute to complete the pantomime show.
In a cruel twist of fate for the visitors, Vale crushed any hope of a late equaliser when Paynter's persistence paid off with a headed tap-in after having his original shot parried by Cutler.