The Blues are looking to become one of a handful of teams to overturn a two-goal first-leg deficit when they resume their last-16 tie with Walter Mazzarri's men.
They were written off by many after their 3-1 defeat at the San Paolo stadium two and a half weeks ago in what was the death throes of Andre Villas-Boas' reign.
Since then, much has happened to give Chelsea hope they may be able to turn the tie around.
Caretaker manager Roberto Di Matteo's first game in charge saw them stop the rot that had set in under Villas-Boas, while Arsenal went agonisingly close to overhauling a 4-0 first-leg deficit against AC Milan.
More importantly, Napoli also shipped three goals in Friday night's Serie A game against Cagliari.
Unfortunately, they also scored six, racking up their sixth successive victory in the process to go into Wednesday night's game in arguably their best form of the season.
But Chelsea midfielder Ramires has refused to be intimidated, pointing out his side beat Valencia 3-0 in their last must-win Champions League game in December.
He told Chelsea's official matchday programme: "We had our opportunities to score in Naples and we didn't take them, but I think if we play well, we will have lots more chances to score at home - especially with the support of our fans.
"I think back to December, when we won the games against Newcastle, Valencia and Manchester City with some excellent performances.
"I don't think it's too difficult to score two goals - or maybe even more - at gome, so that makes me confident we can go through to the next round."
Despite watching his side net six times on Friday night, Napoli boss Mazzarri was far from happy going into next week's trip to Stamford Bridge.
He said: "I got angry because, even if the result was safe, we shouldn't have conceded the last two goals.
"We cannot relax even for a second, because that way we concede. We've got to reflect on that.
"I am not worried about Chelsea, but the fact is we cannot afford similar defensive errors against Chelsea.
"I'm really working on the psychological aspect, which we saw with Milan was an issue against Arsenal.
"We must not start out timid, we must not think about our advantage, but instead immediately play the way we know how.
"Chelsea will have to look for a goal, so I expect them to go on the attack.
"We must focus exclusively on playing our game and trying to score in London without being defensive."
Gianfranco Zola, a hero for both clubs during his playing career, also warned Napoli the tie was far from over.
He told journalists: "It very much depends on the day, whether the Chelsea players will be on fire and maybe the Napoli players will be down.
"Certainly, Napoli has got a big advantage, because tactically they will play the game on their own terms, in the way they want to.
"But that is not an assurance."
Zola admitted his heart was split in two over who he wanted to progress.
"One club has given me the opportunity to play in a big league and has made it happen for me," he said.
"The other one is the team that has given to me everything I wanted to have from a football experience.
"I'm completely divided and I really wish it was the final.
"I really hope that the team that wins has played the best to go through."