The hosts had a Kris Taylor goal disallowed in the 36th minute but a minute before half-time Doug Loft headed in Louis Dodds' cross.
Wolves scored an equaliser 10 minutes after the break when Matt Jarvis dispossessed John McCombe and fired past Simon Tomlinson.
Midway through the half Michael Kightly made his long-awaited Wolves comeback having been sidelined with a broken metatarsal in March.
Despite Wolves increasing the pressure it was Vale who snatched the winner three minutes from time when Robert Taylor latched on to player-coach Geoff Horsfield's flick-on to fire low into the corner.
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