The Addicks squandered a two-goal lead as the visitors fought back to level the scores, but the home side went on to score two more to gain a deserved 4-2 victory.
Veteran midfielder Matt Holland put the home side in front from close range after Reading's goalkeeper Marcus Hahnemann could not hold on to Luke Varney's shot and Holland was on hand to tap home only his 14th goal in 181 Charlton appearances.
Reading had a great chance to level the scores when Kevin Doyle was brought down by Yassin Moutaouakil and he took the penalty himself, but thrashed the spot-kick against the crossbar.
Charlton increased their lead from the penalty spot, Andy Gray making no mistake after Varney had been brought down by Ibrahima Sonko just inside the area.
Sonko redeemed himself in injury time in the first half when he powered home a header after Charlton failed to clear their lines.
Referee Lee Mason then gave Reading a second penalty for what looked like an innocuous challenge by Jonathan Fortune on Leroy Lita.
Charlton keeper Nicky Weaver saved Stephen Hunt's spot-kick, but the referee ordered it to be retaken because Weaver had moved off his line and this time Hunt scored.
Charlton were not to be denied however and Varney restored their lead with a brilliant header from Lloyd Sam's cross and recent signing Hameur Bouazza put the icing on the cake for the home side with a powerful left-foot volley from Nicky Bailey's cross.
Reading's woes were compounded seven minutes from time when Sonko was sent off for a second bookable offence after a reckless tackle.
Charlton boss Alan Pardew, who has had to sell a number of players on high wages, would have been delighted to have got the better of one of the sides he formerly managed.
Meanwhile, Steve Coppell will be wondering how his defence conceded four goals, having kept a clean sheet in their opening two games of the season.