Charlton moved off the bottom of the Premiership after Talal El Karkouri's last-gasp free-kick sealed a crucial and deserved win over Blackburn.
El Karkouri is congratulated by Matt Holland after his late winner
The Addicks had plenty of first-half chances and felt they should have had a 26th-minute penalty when the impressive Lloyd Sam was felled by Lucas Neill.
Charlton's Hermann Hreidarsson headed over on 67 minutes while Blackburn created little after the break.
And El Karkouri fired home deep into injury time with a well-placed strike.
The goal sent a relieved Valley into raptures and head coach Les Reed ran on to the pitch in delight as he celebrated his first win as coach.
It was Charlton's third victory of the season lifted them above Watford on the 14th anniversary of the club's return to The Valley.
The visitors, searching for back-to-back wins after the victory over Fulham at the weekend, started brightly and Morten Gamst Pedersen twice went close early on.
But it was Sam, 22, that caught the eye on his Premiership debut and caused plenty of early problems - including the penalty claim.
And he should have put his side ahead soon after but he blasted over from just eight yards out.
Blackburn striker Benni McCarthy buried his shot in the side netting at the start of the second half after keeper Brad Friedel made a brave save to deny Bryan Hughes at the other end.
The game looked to be heading for a draw but defender El Karkouri had the final say with his curler after Stephane Henchoz had been booked for holding back substitute Marcus Bent.
Charlton head coach Les Reed:
"We deserved it, we played very well and worked very hard.
"When you are at the bottom of the table things do not go for you but maybe this will be the turning point of the season, it has given us the win and the break we needed.
"The home games are important. I have said for the last few weeks that if we win our home games, we will get out of trouble and we had to start tonight."
Blackburn manager Mark Hughes:
"It was a game that had draw written all over it.
"We did not capitalise on the good opportunities we had and if you don't do that you sometimes get hurt by the sucker punch.
"It was a poor goal to concede. We need to be more professional in that respect, at that stage you see the game out and take what you can."
Charlton: Carson, Young, El Karkouri, Hreidarsson, Traore (Diawara 26), Sam (Marcus Bent 71), Hughes, Faye, Kishishev (Holland 88), Reid, Darren Bent.
Subs Not Used: Myhre, Rommedahl.
Goals: El Karkouri 90.
Blackburn: Friedel, Neill, Ooijer, Henchoz, Gray, Emerton (Peter 62), Savage, Bentley (Kerimoglu 46), Pedersen (Gallagher 46), Nonda, McCarthy.
Subs Not Used: Brown, Mokoena.
Booked: Neill, Henchoz.
Ref: C Foy (Merseyside).