Substitute Joel Porter was Hartlepool's match-winner, needing only 20 minutes to turn the game on its head after impressive Rovers looked certain to end the unbeaten home record.
The Australian international scored two late goals to earn Pool an unlikely win which will have surprised even their most optimistic fans.
Their team had looked out of sorts for the second home game running, but once again defied the odds for a vital victory.
Doncaster were clearly the better side long before they took the lead on the half-hour.
Neil Roberts sent an early shot straight at home keeper Dimi Konstantopoulos, who then needed his feet to save Gregg Blundell's shot after another good Rovers move.
Another created the breakthrough when James Coppinger, busy against his former club, crossed well from the right and Roberts was at the far post to grab his first goal for the club.
The home attack looked weak by comparison, though Tony Sweeney's shot was well saved by Michael Ingham and Richie Humphreys sent his effort inches over the bar.
Rovers might have made it two on 39 minutes, though, when the impressive Paul Green got on the end of a sweeping move from their own half only to see his shot hit the bar and go behind.
Pool improved after the break, but lacked bite until Porter arrived on 70 minutes.
He levelled the scores seven minutes later with a looping header into the top corner after a cross from fellow sub Jack Ross.
And with a minute left, Porter grabbed a dramatic winner when he latched on to a long clearance and with Michael Ingham coming off his line, lobbed the keeper from the edge of the area to win the game.