A magnificent long-range half-volley from Dale Stephens gave Charlton a deserved lead and Rovers full-back Martin Olsson, a transfer target for West Ham, cleared off the line from Lawrie Wilson to prevent further damage.
Scotland striker Jordan Rhodes produced a superb diving header to level matters and net his 15th goal in 25 Blackburn appearances but, after Stephens spurned a glorious opportunity for his second, Yann Kermorgant leapt highest to decisively re-establish Charlton's lead in the 64th minute.
Chris Powell's Addicks leapfrog Blackburn to go 12th in the table, while the pre-season promotion favourites lie 10 points shy of the play-off places in 14th.
Simon Vukcevic and Ruben Rochina were off target with speculative efforts for Blackburn during the opening exchanges as Charlton failed to make an early impression in the final third.
Colin Kazim-Richards might have done better when he headed Rochina's corner into the arms of Addicks goalkeeper Ben Hamer before the visitors took a 26th-minute lead.
Charlton full-back Chris Solly burst clear of Kazim-Richards' attentions down the right and his cross was only partially cleared by Olsson, leaving Stephens to emphatically find the top corner from 25 yards.
It should have been two moments later when Rovers keeper Jake Kean denied Johnnie Jackson and Olsson hacked Wilson's follow-up off the line.
A Blackburn response was not forthcoming and boos could be heard from the terraces at the half-time whistle - an atmosphere that made an equaliser three minutes after the restart seem unlikely.
But Rhodes, starved of service during the opening period, had other ideas when he displayed supreme poaching instincts to plant a diving header from Kazim-Richards' right-wing cross beyond the out-stretched Hamer and into the bottom-left corner.
Presented with a far easier chance than the one he opened the scoring with, Stephens should have restored Charlton's advantage moments later but blazed wide with the goal at his mercy after Bradley Pritchard's shot was blocked.
Kazim-Richards drove towards the Charlton box with an hour played and looked to bend into the far corner, finding Hamer equal to the task as he produced an impressive touch behind.
Charlton had two corners of their own after Scott Dann almost diverted Cedric Evina's cross into his own net and they retook the lead when Rovers failed to clear the latter and Kermorgant looped a header home from Pritchard's first-time cross.
Blackburn's response to going behind was more positive on this occasion as Kazim-Richards nodded agonisingly wide at the far post, but their failure to test Hamer in the final 25 minutes was a damning indictment.