Skipper John Terry, striker Didier Drogba and midfielder Frank Lampard, who between them have amassed 235 appearances in the competition, all scored as Chelsea overcame a 3-1 first leg deficit to win 4-1 on the night and 5-4 on aggregate.
Branislav Ivanovic belted home the winner in extra time to break Napoli's resistance but it was the three pillars of their title-winning dynasties who were the driving force as Chelsea stayed on course for the trophy owner Roman Abramovich craves.
Andre Villas-Boas had been hired to build a bright new future at Chelsea but the 3-1 defeat in Naples in February, in which he left Lampard and Michael Essien on the bench, hastened his departure after just eight months in the hot seat.
Under caretaker coach Roberto Di Matteo, Chelsea have won all three matches and the spirit the squad seemed to be lacking under the callow Villas-Boas has returned.
"We are still putting our bodies on the line," Lampard, whose penalty 15 minutes from the end of normal time took the tie to extra time, told reporters.
"We still have the ability in the team to go a long way. You still need the old boys and the experience in the team as well as the young ones coming through.
"As far as Champions League nights go, this one goes right up to the top," added the England midfielder. "To come back from 3-1 down against a quality team like Napoli is pretty special."
The opening 25 minutes on Wednesday did not look encouraging as Chelsea attempted keep the English flag flying in the competition after the demise of both Manchester clubs and Arsenal by becoming only the fourth side to prevail in the Champions League from a two-goal first leg deficit.
Napoli, roared on by 2,500 fans, bristled with attacking intent and wasted several good chances to make Chelsea's task even more daunting, the best of them falling to Uruguayan dangerman Edinson Cavani who could only find the side-netting when sliding in to meet Christian Maggio's cross.
Napoli's failure to capitalise came back to haunt them as Drogba struck with a thundering header after 29 minutes, the 34-year-old launching himself at an in swinging cross from Ramires.
Suddenly there was a spring in Chelsea's step and three minutes into the second half it was Terry's turn to prove his value to the club when he met Lampard's corner with a header that tracked its way into the top corner.
When Swiss midfielder Inler chested down a Terry clearance and hammered a shot past Petr Cech from 25 metres to spark scenes of delirium from the Napoli fans it seemed another night of Champions League pain beckoned.
However, Lampard swept home his penalty 15 minutes from time after Andrea Dossena needlessly handled Ivanovic's header to drag an enthralling last 16 tie into an extra 30 minutes.
Chelsea were not to be denied and seconds before the halfway mark of extra time, Drogba cut back the perfect pass for Ivanovic to rifle an unstoppable shot into the roof of the net.
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