Rovers' first visit to the Keepmoat Stadium ended in a disappointing 2-0 defeat.
An entertaining match in which both teams had a host chances was settled by the side who took theirs - Doncaster Rovers.
Debutant Theo Robinson gave the home side a first half lead, nodding home James Husband's 36th minute free-kick.
Before that Jordan Rhodes had fired narrowly wide after rounding Ross Turnbull in the Doncaster goal, whilst Chris Taylor's header was ruled out for offside.
The second half saw Gary Bowyer's side lay siege to the Doncaster goal but the home side withstood the pressure and scored an unlikely second when Husband's cross from the left flew high into the net.
Robinson saw a second strike ruled out for offside before Chris Brown's close-range effort deflected into the arms of Kean.
The visitors plugged away looking for a route back into the game but were unable to find the shots to test Turnbull as Doncaster held out to claim their first league win of the season.
Rovers made two changes from side that suffered a last-gasp defeat to Nottingham Forest last time out.
Into the side for their first league starts of the season came Tom Cairney and David Dunn with Alex Marrow and Leon Best the men to drop to the bench.
Gary Bowyer predicted that Doncaster would play in the image of their manager and he was certainly right in an entertaining first half.
The game had offered little until the 9th minute when an under-hit back pass from Grant Hanley sold Jake Kean short allowed Chris Brown to steal in, the striker poked the ball goalwards but it rolled agonisingly wide of the upright.
Moments later David Cotterill tested Rovers with a shot from the edge of the box, Jake Kean doing well to beat the ball away.
There was a lively tempo to the game with Doncaster not giving the visitors a moment's peace, Chris Jones fed Theo Robinson but Kean slid out quickly to clear the danger.
Doncaster's incessant pressing saw Rovers have little time on the ball, their best chance of the half coming on 28 minutes when an inch-perfect through ball from Alan Judge saw Jordan Rhodes race clear, he hurdled the wild challenge of 'keeper Ross Turnbull but from an increasingly tight angle the striker fired just wide.
James Coppinger saw a deflected shot on the turn well-saved by Kean, before Grant Hanley missed a great chance to put the visitors in front. Rising high to meet Tom Cairney's corner kick, the Scottish international could only head over the crossbar.
Rovers were made to pay for that miss as Doncaster took the lead on 36 minutes. A free-kick on the right was delivered left-footed by James Husband and Theo Robinson, who only joined from Derby County 24 hours earlier, stole in to head past the helpless Kean.
Rovers tried to respond straight away with a surging run from Todd Kane but the defender was well wide with his shot.
The last meaningful action of the first half saw Rovers put the ball in the back of the net, but it wouldn't count as Jordan Rhodes was offside as he nodded Alan Judge's centre down for Chris Taylor to score.
The opening ten minutes of the second half saw Paul Dickov's side ride their luck as Rovers came out with the intent of getting back on level terms - and quickly.
There were two chances in two minutes for Chris Taylor, the first saw him fire wide after Alan Judge cut inside, the second from a David Dunn cross saw Taylor head across goal but wide.
A Judge free-kick was met powerfully by the head of Hanley but it deflected off Bongani Khumalo and wide, then from the resulting corner the Doncaster defender threw himself at the ball to clear.
A second corner kick came in from Cairney resulting in huge shouts for handball from those of a blue and white persuasion, but referee Geoff Elringham was unmoved, only awarding another corner kick.
This time Judge sent the ball in from the left, Rhodes couldn't connect and a diving Taylor could only put his header wide.
Despite the pressure from Gary Bowyer's side it was the home team who grabbed the second goal just before the hour mark, albeit in fortunate circumstances.
David Cotterill had a little too much space down the right and as he fed James Husband on the overlap the defender's deep cross caught out Jake Kean and the ball looped over the Rovers' 'keeper and into the back of the net.
Bowyer responded by making three changes in quick succession. Corry Evans came on for his debut, replacing the booked Tom Cairney, whilst Leon Best and Josh King replaced Chris Taylor and David Dunn.
Instead it was the home side who could have made it 3-0. A cross from the left dropped invitingly for Chris Brown but his shot on the half-volley deflected straight into the arms of Kean.
Then it was Leon Best's turn to miss a great chance. Corry Evans' clever pass played in Tommy Spurr but as the former Doncaster man sent a delightful ball to the back post Best could only nod down and wide.
Even the effervescent Alan Judge was wasteful in front of goal, a long ball forward flicked on by Best was nodded into the path of Judge by Rhodes, but the Irishman lashed high over the bar.
Then Josh King did well work his way out of trouble to find Judge with a long ball, but the midfielder fired over from long range.
To their credit Rovers never gave up, but with Doncaster drawing strength from their lead, they saw out the danger to claim their first three points of the campaign, whilst Gary Bowyer's side still wait for theirs.
DONNY: Turnbull, Husband, Jones, Khumalo, Wabara, Keegan, Wellens, Coppinger, Cotterill (sub Syers 90+3 mins), Brown, Robinson (sub Duffy 76 mins).
Subs not used: Maxted (GK), Paynter, Quinn, McCullough, Bennett.
Goals: Robinson 36 mins, Husband 58 mins.
ROVERS: Kean, Kane, Dann (c), Hanley, Spurr, Taylor (sub Best 66 mins), Lowe, Cairney (sub Evans 60 mins), Judge, Dunn (sub King 66 mins), Rhodes.
Subs not used: Eastwood, Marrow, Morris, Givet.
Booked: Cairney, Hanley, Taylor
Attendance: 8707 (1454 away fans).