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.
"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."
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.
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.
