The west Londoners overcame the odds at Stamford Bridge to progress to the quarter-finals, overcoming a 3-1 first-leg defeat in Naples to go through 5-4 on aggregate after extra-time.
Didier Drogba, John Terry and Frank Lampard - the men the sacked Andre Villas-Boas seemed so determined to discard - proved just how difficult they would be to replace with a goal each in a thrilling win.
Although Gokhan Inler netted for Napoli at 2-0, Branislav Ivanovic settled the tie before half-time in extra-time on a night every bit as historic as Chelsea captain Terry had predicted.
"For the club, you know, it meant a lot," said interim boss Di Matteo, who ran on to the pitch to embrace the Chelsea players on the final whistle. "To still be able to play in the Champions League, and also you could see how much it meant to the players.
"I think everybody was very happy and delighted that we managed to stay in the Champions League after putting on such a big performance. I've had some great nights, I have to say, but I think it will probably go down in the club's history."
Drogba repeated his desire to stay at Chelsea for "as long as possible" after the inspiring comeback - but said the matter may be out of his hands.
The striker currently looks set to leave the club - seemingly for a lucrative payday in China - when his contract expires at the end of the season following failed negotiations over a new deal.
But he admitted Wednesday night's 5-4 aggregate success made him want to stay put even more, telling Canal+: "I am not master of my fate, but I will stay as long as possible.
"I am happy here, to experience moments like these. I hope there will be many others."
Chelsea became only the fourth team in 45 attempts to overturn a first leg deficit of two goals or more, belying the predictions that Wednesday night would be the likes of Drogba's final Champions League outing for the club.
The Ivorian said: "Many have said that it was my last game, but the adventure continues. It has been a long time since I have seen a Chelsea like this."
The Blues have come under heavy criticism for their performances this season.
Lampard said: "The only way to answer it is to win games and play well and we've done that.
"It was an amazing night here. I've had some very good nights here in the Champions League at home and this one goes straight in right at the top because being 3-1 down against a quality team and performing like we did was a great feeling."