In a lively start to the game, Mark Goodlad was forced into action after only seven minutes when he made two vital stops from Eifion Williams to keep the Valiants on level terms.
Only a minute later, Vale had a chance of their own when Billy Paynter spotted Chris Birchall moving into space on the left of the box but the young winger's shot flew wildly over the bar.
With defender Sam Collins receiving treatment, Hartlepool took full advantage when Eifion Williams seized upon Richie Humphreys' flicked on corner at the back post to give his side the lead after 12 minutes.
After a quiet spell for both teams, Mickey Bell reignited Vale's attacking play when his burst forward resulted in the left-back firing a long-range shot that Dimitrios Konstantopoulos was forced to push around his post.
The home side managed to level the scores three minutes before half time when a flowing move saw Gary Mulligan cross from the right to find Michael Cummins whose powerful header was parried straight back into his path for him to finish second time.
However, Port Vale were soon behind again when after Thomas Butler's 64th minute shot looked to have been tipped on to the crossbar, the linesman judged it to have crossed the line.
The Valiants almost hit back straight away when substitute Craig James fired a volley from 12 yards but Konstantopoulos stayed alert to superbly direct the ball over the bar.
Vale continued to batter the Pool goal to no avail and with only four minutes left on the clock the goalkeeper was the hero again, saving a point-blank Paynter header to give his side the points.