Darren Bent opened and completed the scoring, Danny Murphy ramming home a superb 25-yard free-kick in between, after Darren Ambrose had marred an impressive debut by being sent off in the 55th minute for a two-footed challenge on Stephen Wright.
Bent took just ten minutes to make his presence felt, beating the offside trap to go clear. Kelvin Davis raced from his line and became stranded as defenders raced back to help out but Bent kept his cool to hammer the ball into the empty net.
The Addicks spurned two great chances to go further ahead, Murphy heading over from close range and Ambrose hitting the side-netting from a good position.
Andy Gray headed over from a Dean Whitehead free-kick but Charlton always posed a greater danger in front of goal, Murphy setting up Bent who slipped on the wet surface with the goal at his mercy.
Stephan Andersen saved well from Whitehead but the home side were not to be denied and drew level in the 31st minute. The lively Andy Welsh jinked his way to the byline and after Whitehead's shot was beaten out by Andersen, Gray pounced to force the ball home from a tight angle.
Charlton looked as though they were going to rue their missed chances when they were reduced to ten men. Ambrose, booed throughout following his summer move from Newcastle United, went over the top when challenging Wright and referee Howard Webb immediately reached for the red card.
Sunderland, however, failed to take advantage and were stunned in the 64th minute. Wright fouled Alexei Smertin, and although Davis lined up the wall, Murphy gave him no chance from the resultant free-kick.
Julio Arca and Gray were off target as Sunderland went all out for the equaliser, Stephen Elliott replacing the tiring Welsh, but it was to no avail with goalkeeper Andersen never seriously tested.
To rub salt into Sunderland's wounds, Bent latched on to a long throughball and, after holding off a couple of defenders, fired hard and low across Davis into the far corner of the net.
MAN OF THE MATCH: Danny Murphy (Charlton) - The former Liverpool man pulled all the strings in Charlton's midfield, scored a fine goal and was behind all the Addicks' best attacking moves.