Charlton leapfrogged Tottenham in the league table to pile pressure on Spurs after Jacques Santini's departure.
They cruised into a comfortable 3-0 lead with a Shaun Bartlett brace and a deflected Jerome Thomas shot.
Bartlett scored with a deft volley and diving header before being sent off for deliberate handball - a decision that turned the game on its head.
Robbie Keane converted from the spot and while Jermain Defoe scored a second, Charlton clung on for victory.
Prior to the match Frank Arnesen had addressed the White Hart Lane faithful in an attempt to ease their worries in the wake of Santini resigning.
The club's Danish sporting director described himself as "very optimistic" and urged the crowd to "stand behind the team and give them the 12th man".
But while he was given a rousing reception, his words fell on deaf ears as his team were booed off 45 minutes later.
Santini introduced a battling determination in defence, but the back four stand-in manager Martin Jol sent out were a pale imitation.
Charlton had two efforts on goal in the opening half and turned around two up.
Thomas was a constant outlet on the left and needed no second invitation when Noe Pamarot stood off him to send in an inviting, inswinging cross which Bartlett met ahead of Nouredine Naybet at the near post.
The second came from the other flank, Bartlett the final link in a five-man move.
Chris Perry started the ball rolling and quick, one-touch passing through Radostin Kishishev and Jonatan Johansson set former Tottenham player Luke Young free on the right, his pinpoint cross being headed home by Bartlett at the far post.
It had all been embarrassingly easy and Charlton made it three when Thomas got on the scoresheet.
The former Arsenal player exchanged passes with Bartlett on the edge of the area before lining up a shot at goal that deflected past Paul Robinson off Ledley King.
While defence had been a strength under Santini, it was their aimless attacking ambition that attracted criticism.
With the game seemingly up, they finally had a telling effort on goal, Fredi Kanoute's speculative long-range effort hitting the woodwork.
And they were gifted a way back into the game when Bartlett handled a goal-bound effort on his own line. The South African saw red and Keane converted from the spot.
Having booed their side off, the Tottenham fans finally heeded Arnesen's words and made a telling contribution urging their side forward in a grandstand finish.
And they were rewarded with another goal when Matt Holland hopelessly under-hit a back pass. Keane pounced and freed Defoe who swivelled and shot beyond Dean Kiely.
In a helter-sketler finish Jason Euell missed a golden chance to seal the points and Kanoute shot narrowly wide.
However, that was as close as Spurs came in their search for an equaliser as
Charlton clung on for their first away win of the season.
But while Tottenham reflect on another defeat, Arnesen and Jol must have seen some cause for optimism in their side's fighting finish.
Tottenham: Robinson, Pamarot, Naybet, King, Bunjevcevic, Davies (Ziegler 45), Pedro Mendes, Redknapp (Carrick 59), Keane, Kanoute, Defoe. Subs Not Used: Keller, Brown, Silva Sousa.
Goals: Keane 69 pen, Defoe 79.
Charlton: Kiely, Young, Perry, El Karkouri, Hreidarsson, Kishishev, Holland, Murphy (Fortune 89), Thomas (Konchesky 84), Johansson (Euell 81), Bartlett. Subs Not Used: Jeffers, Andersen.
Sent Off: Bartlett (68).
Booked: Thomas, Young.
Goals: Bartlett 17, 39, Thomas 50.
Ref: N Barry (N Lincolnshire).