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United missed a series of chances and were punished when Gregg Blundell grabbed the winner for Doncaster in an action packed second half.
The first half was scrappy as both sides battled for possession but the visitors had an edge with Steve Torpey and Steve MacLean both going close on several occasions.
MacLean seemed to miscue when he fired wide in the eighth minute as he set the pattern for a number of wasted opportunities in front of goal.
Torpey did get the ball in the net in the 17th minute only to be ruled offside and he had a fierce shot tipped past the post by Rovers keeper Andy Warrington a minute later.
Doncaster could not seem to settle into a rhythm during the first half and only threatened in patches.
But they should have scored in the 19th minute when Michael McIndoe and Blundell cleverly created a chance for Francis Tierney who flicked the ball wide from close range.
MacLean hammered a shot over the top a couple of minutes later and Leo Fortune-West headed over the bar at the other end as play switched quickly.
But the best chance of the first half fell to United's Matt Sparrow who somehow managed to head wide at the far post from Lee Featherstone's pinpoint cross with the goal gaping.
Sparrow was out of luck again when he saw a shot saved by the legs of home keeper Warrington just before the interval.
Rovers stepped up a gear in the second half and Fortune-West headed against the post following a 61st minute corner.
Adriano Rigoglioso made a difference after coming on for Rovers in the 66th minute and he put Blundell through to fire home from close range a minute later.
Torpey missed a great chance to equalise in the 74th minute and Sharp had a cracking free-kick tipped over the bar three minutes from time.
But Doncaster held out with McIndoe going close to adding a second in injury time.