Vale's early play gifted them several opportunities and they could have found themselves a goal to the good when Ian Armstrong cut inside from the left to provide Stephen Brooker with a shooting chance but his shot fell wide off Boaz Myhill's goal.
However, against the run of play Hull took the lead in the 14th minute when Stuart Elliott played the ball through for a totally unmarked Nick Barmby who had all the time in the world to lash his half volley into Jonathan Brain's top left from 15 yards.
The Valiants continued their assault despite the blow and soon got back on level terms 11 minutes later when Craig James' wicked left-footed free kick was parried by Myhill and pounced upon by the awaiting Sam Collins from close range.
Martin Foyle's side came out all guns blazing after the break and soon took the lead six minutes in after Armstrong squeezed through a pass for Brooker who despite being under pressure hammered home the ball leaving Myhill no chance.
Hull piled on the pressure late on and thought that they had snatched a point in stoppage time when good work by Jonathan Walters on the left of the box helped the ball into the centre and after a hectic couple of seconds, Elliott popped up to finish under Brain.
Brooker silenced the visiting fans almost instantly though when Steve Rowland headed the ball back into the mixer for the striker who kept his balance and slotted the ball past the oncoming keeper.