The England Under-21 hit-man, who left The Addicks under a shadow to join West Ham, silenced the boos of the home fans with his side's second, although the visitors were left to hold on nervously after coasting into a three goal lead.
Spurs served notice of their attacking intent when Ledley King had the first real shot in anger after just four minutes. Dean Kiely was happy to see his skidding 20-yard shot fly narrowly wide, and The Republic of Ireland custodian then had to be alert to push a powerful effort from Defoe away for a corner shortly afterwards.
However, there was nothing the keeper could do just two minutes later as Spurs hit the front. Paul Konchesky, who had a loan spell at White Hart Lane earlier in the season, endured a personal nightmare as his poor back header presented Simon Davies with a clear run on goal, and, as Konchesky charged back to try and block the Welshman's shot, he succeeded only in deflecting the ball past Kiely and in off a post.
Konchesky nearly helped make amends on the quarter hour mark, playing in Shaun Bartlett with a neat through ball, but the South African's weak attempted pull-back for Carlton Cole was intercepted by Kasey Keller.
Graham Stuart came close to restoring parity with a volley after Gary Doherty had headed a Claus Jensen corner to him on the edge of the box, but his strike bounced back out off the post after a crucial touch from Keller.
Two minutes later and the visitors led by two; Keller released Davies down the right with a quick throw-out and the midfielder was allowed to progress deep into the Charlton half before delivering a low cross which Konchesky could only help into the path of Defoe who finished at the second attempt with his head after initially being denied by Kiely.
Charlton almost found a way back into the game just moments later, but Carlton Cole saw his effort cannon back off the bar after he redirected Konchesky's fierce centre, and Graham Stuart then saw an effort controversially chalked out for offside with the last kick of the first period.
Things got even worse for Alan Curbishley's men just seconds into the second half as Spurs seemed to have all but killed the game as contest, Ledley King latched on to Chris Perry's half-clearance to drill low past Kiely from fifteen yards.
The hosts reacted well, though, and Graham Stuart reduced the arrears almost instantly when he lashed home from 12 yards through a crowded penalty area after the visitors could only half clear a left-wing corner.
The groans of the Spurs fans were almost audible ten minutes from time when their on-loan defender Chris Perry made it 3-2 with a well-directed header from substitute Paolo Di Canio's cross. Memories of Manchester City's miraculous 4-3 comeback must have been to the fore, but Johnnie Jackson ensured they could breathe easy four minutes later with his first senior goal for the club.
The left-sided midfielder collected King's pass and raced goalwards before unleashing a magnificent 20-yard strike into the corner which left Kiely grasping thin air.
The win takes Spurs up to 11th, and to within four points of their opponents who have now lost three games on the spin since selling Scott Parker to Chelsea.