After 14 kicks were converted, Kolo Toure and Gervinho failed to find the target for the Elephants as Zambia's Rainford Kalaba also blazed over. But Stoppila Sunzu found the top corner to complete an amazing 8-7 victory. It was a heartbreaking end for Ivorian skipper Didier Drogba, who missed a spot-kick in normal time.
It means the wait goes on for an Ivory Coast team replete with many Premier League and European stars, with the country losing the 2006 final to Egypt in the same way and last winning the tournament 20 years ago.
But for the Chipolopolo, who have already been runners-up twice, it concluded a tournament where they were inspired by the loss of the 1993 Zambian team after a plane crash close to the venue of the final in Libreville.
The last time the southern African country reached the final was in 1994, a year after 18 Zambian teams members died as they took off from the Gabonese capital.
En route to the final, the current team had spoken of the strength they had gained in remembering that tragedy.
And in winning the shootout, they showed a steely determination to beat their supposedly more illustrious opponents with a performance that was built on an indefatigable sprit.