The front man pounced to fire home what proved to be the only goal of the game but Pools could easily have scored more if they had been more ruthless in the final third.
Pools carved out the first chance inside five minutes as Jordan Richards corner from the left fell kindly for Kenton Richardson but the youngster lashed a shot in to the side netting.
Jake Orrell used his pace to get away down the left and fed a ball inside for Devante Rodney who took a touch away from the defender but saw his powerful drive parried by keeper Laurence Bilboe.
The visitors’ first chance came after a clever ball over the top set Akeel Francis through on goal but, with young keeper Ryan Catterick off his line, the front man miscued his attempted lob and it well wide.
Seconds later Nicky Deverdics was denied by a great save from Bilboe when the Pools midfielder got in at the far post only to see his downward header clawed away from danger.
There was another opportunity for Francis to open the scoring when he again got away from the Pools defence but his time he prodded an effort over the bar.
Orrell was causing problems for the Rotherham defence on the left flank and, after cleverly weaving his way through, Bilboe did well to get down and save his low shot.
However, the breakthrough arrived seven minutes before the break and Orrell was at the centre of it with another determined run at the end of which his shot was parried by Bilboe but Rodney was in the right place to rifle home the rebound.
Pools could have extended their lead when another Deverdics header came back off the cross bar, while the midfielder then turned provider with a clever pass round the corner for Jordan Richards but the full-back’s shot was well smothered by the keeper at the front post.
Ian McGuckin’s side then controlled things after the break and dominated possession against their visitors, though they didn’t create as many clear cut opportunities to score.
Josh Hawkes sent an effort just wide from the edge of the box after some good build-up play, while substitute Connor Smith flashed another shot a little off target from distance.
With time running out Rotherham substitute Reece McGinley almost helped engineer an equaliser when he wriggled clear of the Pools defence to set up Francis but the striker was denied by a brilliant reaction save from Catterick.
Pools responded by coming close to extending their lead when Richards drove to the byline before cutting the ball back for Richardson but his drive was held by Bilboe.
And the Millers keeper had more work to do right at the death when he got behind a Hawkes shot after a clever flick from Smith had set the young midfielder away.
Full Time: Pools 1 Rotherham United 0
Pools: Catterick, Richards, Martin, Skidmore (Elliott 56), Wise, Pollock, Richardson, Deverdics, Rodney (Smith 46), Hawkes, Orrell.
Subs not used: Dudzinski, Assenso, Turnbull.