Serbian international Ivanovic swept home emphatically in the 105th minute to give Chelsea - beaten 3-1 by the Italians in last month's first leg in Naples - a 5-4 aggregate victory at Stamford Bridge.
It was only the fourth time in the modern history of the Champions League that a team has successfully overturned a two-goal first leg deficit.
The match had gone to extra-time after a pulsating period of 90 minutes which saw Chelsea battle to a 3-1 win that left the tie locked at 4-4 overall.
Chelsea had taken a 2-0 lead on the night through headers from Didier Drogba and John Terry to put the Blues ahead on away goals.
But Gokhan Inler restored Napoli's crucial advantage with a 55th minute strike before a Frank Lampard penalty 15 minutes from time hauled Chelsea back into the tie to electrify a crowd of 37,784.
Lampard was delighted with the victory and believes it can be a platform for greater things.
Having weathered an early Napoli storm, Chelsea then grabbed the goal their fans had been craving.
Ramires swung in a perfectly flighted cross from the left and Drogba timed his run to perfection before heading powerfully past De Sanctis to trigger bedlam at the Bridge.
The goal signalled the start of Chelsea's best period of the half, with Sturridge flashing a shot across the face of goal which Hugo Campagnaro turned behind nervily.
Chelsea started the second half as they had finished the first, and within two minutes had surged into a 2-0 lead to leave them ahead on the away goals rule.
Lampard swung a corner in from the right and Terry timed his run to perfection to glance a looping header up and over De Sanctis.
Yet just as it seemed as if Chelsea were ready to take an unassailable grip on the tie, Napoli clawed their way back into the contest with a moment of brilliance from Inler.
A headed clearance from Terry found the Swiss international on the edge of the area and the midfielder controlled the ball on his chest before driving home a thunderous shot from the edge of the area.
The goal silenced Chelsea but slowly the Londoners regained their momentum, with Ivanovic and Drogba both threatening.
On 74 minutes the Napoli defence cracked when substitute Andrea Dossena handled Ivanovic's header for a certain penalty.
Lampard stepped up to drive in the spot-kick and Chelsea were back level at 4-4 on aggregate to set up extra time and Ivanovic's winner.
ORIGINAL SOURCE
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