Hartlepool were relegated to League Two after failing to earn the win they needed to give themselves a chance of avoiding the drop.
Joel Porter had two early penalty appeals turned down for the home side.
But the visitors took the lead with a low shot from the edge of the area by Michael Cummins.
Pools hit back with five minutes left through James Brown after Mark Goodlad could not hold a Butler shot but there was to be no happy ending.
Hartlepool: Konstantopoulos, Darren Williams, Nelson, Clark, Humphreys, Butler, Sweeney (Brown 79), Bullock (Boyd 68), Robson, Proctor (Eifion Williams 59), Porter.
Subs Not Used: Provett, Turnbull.
Booked: Nelson, Clark.
Goals: Brown 86.
Port Vale: Goodlad, Abbey, McGregor, Pilkington, Jason Talbot, Cummins, Dinning, Togwell, Cardle (Briscoe 71), Constantine, Jeff Smith.
Subs Not Used: Brain, Sam, Christian Smith.
Booked: Constantine, McGregor.
Goals: Cummins 77.
Hartlepool are relegated
Ref: R Booth (Nottinghamshire)