Liam Hatch struck the winner as Darlington came from behind to win.
Vale took the lead after 27 minutes when Luke Rodgers curled a free-kick into the far corner.
But their lead was short-lived, with the home side level nine minutes later when striker Franz Burgmeier fired home a free-kick of from a tight angle.
The visitors were made to pay for missed chances when Hatch headed home Adam Griffin's corner from eight yards to end Vale's unbeaten away record.
Darlington: Brown, Austin, White, Foster, Purdie, Poole (Griffin 23), Kennedy, Ravenhill (Hulbert 58), Burgmeier, Clarke (Blundell 81), Hatch.Subs Not Used: Kazimierczak, Proudlock.
Goals: Burgmeier 38, Hatch 77.
Port Vale: Anyon, Griffith, McCombe, Prosser, Collins, Richman (Perry 87), Taiwo (Davidson 71), Howland, Dodds (Taylor 61), Richards, Rodgers.Subs Not Used: Martin, Lawrie.
Booked: Richman, Prosser, Collins.
Goals: Rodgers 28.
Att: 3,040
Ref: Karl Evans (Greater Manchester).
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