In the end Clive Mendoca's glancing header in the eighth minute proved enough to separate the sides but the outcome was in doubt until the last as chances came and went at both ends in a frantic finale.
After the disappointment of Sunday's FA Cup semi-final defeat by Arsenal, a dank and drizzly evening at The Valley was probably not what Wolves would have wished for little more than 48 hours later. Mendonca's goal was symptomatic of their own early sluggishness and Charlton's greater urgency in the first half hour.
A powerful drive by Shaun Newton had already made Hans Segers scramble to his left to save Wolves but Charlton, seeking their fourth consecutive win in the League, were not to be denied for long. Two minutes later Newton swung over a curling left-footed cross and Mendonca climbed high above a static Wolves defence to guide a perfectly directed header beyond Segers' despairing dive.
Paul Mortimer, twice, and Keith Jones were both close to increasing Charlton's lead with well-struck shots from distance. A better chance fell to Steve Jones, who headed inches wide from Danny Mills' cross.
Wolves kept Charlton at bay for a while but the home side rallied and in first-half injury time Mendonca should have scored again but he slipped in the penalty area mud as he was about to shoot.
Wolves began the second half in a more positive fashion but, just as he had at Villa Park, Mark McGhee withdrew his most potent attacking force, Don Goodman, relatively early in the piece. His replacement, Dougie Freedman, almost justified his manager's decision straight away as he chased after an astute chip through from Paul Simpson, but Sasa Ilic was out quickly and bravely to claim the ball at Freedman's feet.
Mendonca then squandered another opportunity, shooting weakly at Segers after being set up again by Newton. Steve Jones fired just over and three minutes from time Ilic thwarted Freedman again, parrying his shot to safety.
The ensuing corner produced an almighty scramble and even then the substitute Neil Heaney had a chance to wrap it up for Charlton in the dying seconds but he shot straight at Segers.
Charlton (4-4-2): Ilic; Mills, Rufus, Youds, Bowen (Brown, 81); Newton, Kinsella, K Jones, Mortimer (Heaney, 86); Mendonca, S Jones (P Emblen, 89).
Wolves (4-4-2): Segers; Muscat, Williams, Curle, Naylor (Simpson, 29); N Emblen, Osborn (Slater, 79), Sedgley, Froggatt; Goodman (Freedman, 54), Claridge.
Referee: F Stretton (Nottingham).