Nineteen years after a plane crash which killed 18 members of their squad in Libreville, the Chipolopolo returned to the Gabon capital to record the most famous victory in the country's history.
A dramatic shoot-out at the end of 120 minutes of largely underwhelming football went the way of Zambia when Gervinho shot wide and Stophira Sunzu stepped up to slot home.
The final proved a tale of penalty woe for Ivory Coast, chasing their first continental crown for 20 years, with Didier Drogba also failing from the spot during the 90 minutes.
But the win was ultimately no more than Zambia deserved for a plucky display against the odds.
The underdogs started brightly and almost claimed a second-minute lead, Nathan Sinkala's low drive superbly saved by Ivory Coast goalkeeper Boubacar Barry low to his right.
Zambia boss Herve Renard was forced into a reshuffle after 11 minutes when defender Joseph Musonda was forced from the field in tears after catching his knee in the turf when making a challenge.
Nyambe Mulenga came on but the change did not disrupt the Zambians' flow, with Chisamba Lungu looping a header narrowly over two minutes later.
It took Ivory Coast's star-studded line-up 30 minutes to create a noteworthy chance, a clever backheel from Drogba picking out Yaya Toure but the Manchester City midfielder failing to find the target from eight yards.
The match degenerated into a scrappy affair after half-time with neither side able to put together a period of sustained pressure.
But in a rare moment of quality, Gervinho provided Drogba with the chance to redeem himself for his penalty shoot-out miss in the 2006 final defeat to Egypt.
The Arsenal forward burst into the area and was felled by a combination of Isaac Chansa and Mulenga, but Drogba sidefooted his spot-kick horribly over the bar.
The Elephants had another chance to win it in normal time but substitute Max Gradel, having turned his man inside the area, shot inches wide of the far post.
Zambia also had a late chance with a wonderful tackle from Kolo Toure preventing Emmanuel Mayuka from getting a shot on goal when he was well placed.
Zambia had the only chance in the first period of extra-time and it almost resulted in the opening goal.
Felix Katongo beat his marker down the right and crossed for brother Christopher, whose close-range shot would have sneaked in at the near post but for a vital touch from Barry's boot.
Ivory Coast had two chances to win it after the break but Didier Ya Konan curled an effort just wide while, after 117 minutes, Gradel took an airshot when well placed.
The shoot-out was locked at 7-7 after 14 nerveless penalties before Kolo Toure saw his effort saved by Kennedy Mweene.
Rainford Kalaba fluffed his big moment by shooting over the bar but there was no second reprieve when Gervinho missed and Sunzu slotted in.
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