A last-minute goal from Rovers' Liam Mandeville saw Pools defeated 2-1 at the Keepmoat Stadium.
The game started out at a quick pace, with both teams looking bright, and the quick tempo continued throughout the first half.
Pools were the first to test the waters going forward, winning two corners in the first ten minutes.
But it was the hosts who had the first shot of the half with a weak effort that rolled into the arms of Trevor Carson. While the chance did little to really test the keeper, it did signal the start of a strong spell of pressure from Rovers.
James Coppinger had a good chance on goal, running in to power onto a loose ball but Jordan Richards got himself in the way to deflect it out for a corner.
The hosts had the ball in the back of the net on 14 minutes but thankfully the effort was ruled out for a foul on Toto Nsiala in the build-up.
But Rovers were very strong on the attack and Pools had to defend in numbers for large spells of the first half, leaving Amond to chase after any clearances.
There was a blow for Rovers just after 20 minutes when keeper Marko Marosi had to go off after being unable to shake off the effects of a knock to the head. His replacement Ross Etheridge came on and sent his first clearance straight out to Amond.
The Pools striker showed real a cool head to take it back towards goal before chipping a well-placed effort over the keeper but could only watch on as the ball hit the far post.
And from that chance, Rovers burst straight up to the other end of the field to open the scoring; the lively Coppinger sent a lovely cross into the box where John Marquis was waiting to hit home, making it 1-0.
Doncaster Rovers dominated much of the play following the goal but Pools showed a dogged attitude and plugged away when possible.
And it was on one such occasion that the equaliser arrived. Padraig Amond picked up possession inside the box only to be flattened by Matt Baudry with a clumsy challenge.
The referee pointed to the spot and, after another delay for treatment to the keeper – this time sub stopper Etheridge, Amond stepped up and fired home to make it 1-1 just before half time.
Pools started the second half strongly and Amond could well have had his second just after the re-start as he met a Lewis Alessandra cross to volley on goal but his shot found the arms of Etheridge.
And Pools’ pressure was short-lived as Rovers were soon back on the attack, with James Coppinger at the heart of everything for the hosts.
The Rovers skipper linked up neatly with Marquis as the pair floated into the box but the final shot from Marquis went over the bar under pressure from Richards.
Carson then pulled off a great save to deny Coppinger who had powered into the box in search of a goal, while Nsiala followed it up with a great block to deny the Rovers man with the rebound.
By this point, Doncaster were well on top, with Pools pinned back inside their own half and Toto Nsiala came to the rescue a few times, getting in the way with a succession of blocks to deny the hosts.
Matthew Bates was next to step up as he twice denied John Marquis from crossing into the box from the left, while Carson made his second save in collecting a Jordan Houghton strike from distance.
Nicky Deverdics got some space at the right end for Pools and wriggled his way forward to curl an effort at goal which just went wide of the far post.
There was a slight break in the pressure for Pools after that as they started to see more of the ball inside the Doncaster half, winning a couple of corners to give the home defence some work to do.
But just as Pools looked to have stuck in for a point, Rovers made their next attack count in the 90th minute as Liam Mandeville pushed forward into the box to slot home the late winner.
It was a real blow for Pools who had battled hard all the way in this game only to be undone in the final minute of the game.
Full Time: Doncaster Rovers 2 Hartlepool United 1
Attendance: 5009 (661 Pools)
Booked: Nsiala (86)
Doncaster Rovers: Marosi (Etheridge 22), Alcock, Baudry, Butler, Mason, Houghton, Blair, Rowe, Coppinger (Keegan 90), Mandeville, Marquis.
Subs Not Used: Wright, Beestin, Longbottom, Evina, Garrett.
Pools: Carson, Richards, Bates, Nsiala, Carroll, Featherstone, Laurent, Hawkins (Woods 63), Alessandra (Paynter 82), Amond, Deverdics (Jones 88).
Subs Not Used: Bartlett, Harrison, Oates, Orell.