After a goalless draw in Libreville - during which Drogba cannoned over from 12 yards - Stophira Sunzu netted the winning penalty in an 8-7 shoot-out triumph after Premier League duo Kolo Toure and Gervinho missed theirs.
It is heartbreaking for the Elephants, widely regarded as having the best set of players in Africa but constantly unable to translate their personnel advantage into silverware.
They lost the 2006 final to Egypt in similar circumstances, and with Drogba missing then there appears to be a mental problem in the biggest games.
The irony is that Ivory Coast were excellent throughout the tournament: aside from the shoot-out, they did not concede a goal in six matches and become the first side to do so without winning the tournament. It is now 20 years since their only success in the competition when they won it in Senegal in 1992.
But Zambia’s victory is in keeping with the upset theme of these finals, co-hosted by minnows Gabon and Equatorial Guinea, who both surprisingly reached the knockout stages: traditional heavyweights Egypt, Nigeria and Cameroon did not qualify; Senegal, Morocco and joint-favourites Ghana all fell to so-called inferior opposition.
Underdogs from the start, Zambia’s joy at victory was unbridled - the country is still scarred by the 1993 air disaster when almost their entire squad of elite players was wiped out: they almost avenged it the following year, but lost in the final.
The match itself was a cagey but high-quality affair, with both sides excellent at the back and inventive going forward: Ivory Coast paid the price for a lack of urgency though, only really hitting their stride in extra time as their bigger names underperformed in the heavy rain.
The first half was played at a high pace with plenty of endeavour, but stout defending - from Zambia in particular - limited much of the goalmouth activity to half-chances.
Having surprised everyone at these finals it was perhaps of little surprise that Zambia were the more dangerous, as Nathan Sinkala fired at Boubacar Barry on two minutes, while Emmanuel Mayuka - Zambia's only Europe-based player rewarded with a start after netting the winner against Ghana - headed just over soon afterwards.
Rainford Kalaba’s deflected shot almost beat Barry, while later he shot straight at the keeper with better options for the pass.
It was not all good for Zambia though as they lost defender Joseph Musonda to a serious-looking knee injury early on: the veteran attempted to play on and was inconsolable when his match ended, weeping into his shirt as Drogba attempted to reassure him.
It was also not all Zambia as, with more of the possession but fewer chances, the Ivory Coast did actually fashion the best opportunity, the otherwise quiet Yaya Toure putting a low drive wide after Drogba set him up with a clever backheel.
That incident was a rare moment of class for the Elephants’ most heralded players as they struggled to get into the game in the heavy rain, although Gervinho and Saka Tiene were impressive out wide.
With the slightly undersold Stade d’Agondje expecting more of the same, the second half started slugglishly as the pace slowed remarkably and the chances dried up.
That changed on the hour mark as Zambia had a couple of sighters when Chansa’s shot was deflected wide, with the corner that followed also causing problems.
The outsiders were buoyed and went close once more as a low Mayuko ball fizzed across the box, Jean-Jacques Gosso putting it behind just as Christopher Katongo was set to finish.
Elephants coach Francois Zahoui injected some enthusiasm into proceedings by introducing former Leeds winger Max Gradel, now at St Etienne, for an annoyed Salomon Kalou, another anonymous star for the Ivorians.
Gradel almost had an immediate impact, his mazy run causing problems, but it was another wide-man who gave them the opportunity to take charge of the final with 20 minutes left.
Gervinho, criticised for his performances before starring in the semi-final win over Mali, had been the Elephants’ best attacking player and his direct run provoked two rash challenges as Chansa and Nyamba Mulenga lunged into the Arsenal forward.
The referee pointed to the spot and Drogba stepped up: he had already missed one spot-kick at these finals and, infamously, fluffed his lines against Egypt in the 2006 final.
The skipper continued his poor run from the spot by blasting a dreadful penalty well over the bar, nerves appearing to get to the Chelsea star once again in Africa.
As the match approached its latter stages the play became more fraught, with Ivory Coast having more possession but only a dragged effort wide by Gradel to show for it.
Yaya Toure, who barely made an impact, was withdrawn for the lively Bony Wilfried, while his brother Kolo Toure made some timely interventions as Gosso’s forays forward left the defence exposed.
Indeed, the Manchester City defender denied Young Boys forward Mayuka a winner in injury time, his superb hooked clearance compensating for slack marking to let him in initially.
The final whistle came, and extra-time once more beckoned: Ivory Coast’s last two finals in 1992 and 2006 had ended thus, with penalties the inevitable dramatic climax.
Zambia started cagily but they were agonisingly close to taking the lead when the Katongo brothers dovetailed superbly, Felix’s great run and low cross met by Chris at close range but denied by a wonderful stop by Barry, whose foot flicked it on to the post and wide.
That was an anomaly though as both sides seemed more worried about not messing up than actually trying to win the game: the closest anyone came to another chance in the first half of extra-time was when Drogba showed his fleeting quality to control a long ball, forced out of it by keeper and defence, while Gervinho’s weak shot was blocked after a promising run.
The second additional period did see Ivory Coast go close again, as Hannover's Didier Ya Konan - on as a sub - fired inches over from range.
The Elephants were finally starting to dominate, but Zambia were not exactly tiring as they showed with several dangerous counter-attacks.
The final big opportunity fell to Ivory Coast as a Drogba flick-on caused havoc, Gervinho bravely challenging Kennedy Mweene, who was previously excellent but flapped into Gradel’s path, the winger unable to finish.
The lottery of the shoot-out beckoned and it started in typical African fashion - top-notch spot-kicks as no-one missed for 14 efforts, including a cool, rolled finish from goalkeeper Mweene as it entered sudden death.
Then the drama set in. At 7-7 Manchester City defender Kolo Toure - one of the players of the tournament - took a huge run-up before hitting a low shot that Mweene read, palming out in delight; but Kalaba responded with a miss of his own, blasting over as his team-mates sung in support.
It mattered not though as Arsenal’s Gervinho, who looked nervous, ballooned his kick over, leaving defender Sunzu with the chance to make history.
And the full-back, who plies his trade in DR Congo for TP Mazembe, made no mistake as he smashed the ball into the roof of the net, leaving the small but excitable Zambian contingent in raptures as the players lofted French boss Herve Renard on their shoulders.
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