On-loan left-back Alan Sheehan pinched three points for Leeds United with a magnificent first-half free-kick.
But it was a case of smash-and-grab after Doncaster had dominated for most of the match.
Rovers produced some slick passing and classy football but were guilty of wayward finishing and trying to walk the ball into the net at times.
The home side began in confident style but could not find a way passed impressive visiting keeper Casper Ankergren.
Paul Heffernan and James Coppinger worked a neat move in the eighth minute which led to a chance for Jason Price, but his final shot was blocked.
Heffernan hit a shot on the turn just wide four minutes later and was halted by good defending by visiting skipper Jonathon Douglas when another chance beckoned.
Ankergren came to the rescue when he raced to the edge of the box in the 16th minute to save at Heffernan's feet after he had been put clean through by skipper Adam Lockwood.
But despite the Doncaster pressure, it was Leeds who scored against the run of play in the 20th minute when Sheehan curled a 20-yard free-kick over the defensive wall and into the top corner with his left foot.
Rovers immediately tried to hit back when Coppinger dribbled through on the left a minute later, but his close-range shot was kept out as Ankergren reacted instinctively.
The home side suffered a blow when Lockwood was stretched off in the 32nd minute with a suspected fractured foot, but they continued to apply pressure and were unlucky not to be awarded a penalty when Price was bundled over in the box a couple of minutes later.
Leeds defended heroically when they came under intense pressure in the second half but rode their luck when Bradley Johnson headed off the line from Gareth Roberts in the 47th minute with Ankergren beaten.
Another penalty appeal was waved aside when Steve Roberts was bundled over in the area in the 67th minute and substitute Lewis Guy missed a great chance when he fired over the top in the closing stages.
Rovers were denied the equaliser they deserved in stoppage time when Douglas cleared off the line from Paul Green in the last move of the match.