Andy Gray headed them in front from a third minute free-kick but they had their backs to the wall for the rest of the game before clinching their first away win.
Doncaster Rovers were full of invention and skilful soccer but they just could not put the ball in the back of the net.
It was not for want of trying as they enjoyed a vast amount of possession and built up their attacks cleverly, although they found the Charlton defence a tough nut to crack.
Rovers have conceded three goals from free-kicks already this season and their misery at set-pieces continued when Gray headed home after the ball had been played deep into the Doncaster penalty area by Jonathan Fortune.
Doncaster had started like a train and went close in the first minute when Martin Cranie did well to block a goalbound shot from Lewis Guy.
It was all Doncaster after Charlton had scored but their attack lacked a cutting edge.
Richie Wellens was out of luck with a superb volley following a corner which was tipped over by Nicky Weaver in the 20th minute.
James Hayter looked to have Weaver beaten with a header following another corner in 35th minute, only to see the ball bounce back off team-mate Guy who had somehow got in the way.
Charlton relied on counter attacks for their attempts at goal and Lloyd Sam cut inside from the right just before the interval to hit a low shot into the sidenetting.
Rovers continued to pile on the pressure in the second half, but Gareth Taylor missed a good chance when he beat the offside trap but fired well off the mark after good work by Wellens in the 56th minute.
The home side continued to have no luck at all in front of goal and almost conceded a second eight minutes from time, when Charlton broke away with Luke Varney firing just wide after good work from Hameur Bouazza and Nicky Bailey.