Federio Macheda returned to haunt his former club with a ruthless brace at the Keepmoat Stadium.
Doncaster Rovers had looked on course to maintain their impressive unbeaten home record when Paul Quinn blasted them into a 37th minute lead.
However, Macheda's second-half double sandwiched in Lee Novak's 11th of the season to wrap up a crucial haul of maximum points for Lee Clark's side.
This was always set to be an intriguing encounter. Rovers were unbeaten in their last eight on home turf while Blues held one of the best away records in the Sky Bet Championship.
Clark had called for his side to build on a clean sheet in south Yorkshire having seen his team cheaply leak goals in the last few matches. They initially looked set to do exactly that as the visitors were comfortable early on and controlled large parts of the game in the opening half-an-hour.
Chris Burke went close in the 14th minute with a curling effort from the right that whistled just past the far post, while at the other end Doncaster had been limited to hopeful efforts from David Cotterill and James Coppiner, playing his 400th game for Rovers, that ended up high and wide.
However, despite that comfortable start from Blues, it was the hosts who took the lead. Cotterill's free-kick into the Blues box was nodded down by Chris Brown, Lucas Neill teed up Quinn whose initial shot was blocked but the follow up gave Darren Randolph no chance.
Blues needed to come out fighting in the second-half and they did exactly that with Nikola Zigic being introduced for Jordon Ibe at the break.
But arguably the turning point of this game was a superb save from Randolph in the 50th minute. Cotterill's free-kick from the left gifted Neill a point blank header from six yards but some how Randolph managed to tip the effort clear.
Blues clearly weren't prepared to let this away day slip away from them and that was epitomised by Macheda's 57th minute opener. The tenacious Italian, who enjoyed a loan spell at Rovers earlier this season, forced James Husband into gifting him possession in the Doncaster box and he cooly slotted past Sam Johnstone from a narrow angle on the right.
From that moment onwards, Blues were homing in on another victory on the road. While Randolph had played another vital role between the sticks, he also contributed to Blues' second in the 72nd minute. The Republic of Ireland international's long ball from the back bounced favourably down the left, Novak didn't give up the chase and calmly prodded an effort beyond the outcoming Johnstone. Quinn initially looked to have got back to slide the effort clear but only ended up sliding the ball into the net.
Any lingering nerves in the Blues camp were lifted in the 76th minute when Macheda completed his fruitful return to the Keepmoat Stadium. Paul Robinson's free-kick from the right found the head of Tom Thorpe and Macheda arrived yards out to glance home in front of the 1,648 travelling Bluenoses.
Doncaster had their chances to reduce the deficit. Cotterill's cross from the left failed to get a clear connection with the head of substitute Theo Robinson six yards out in the 79th minute.
Robinson did connect with the ball deep into injury time but Randolph was again alert to palm away his thumping effort from four yards out.