The Blues travel to Italy for the first leg of their last 16 tie on Tuesday night looking to keep alive their hopes of winning one of the two trophies realistically available to them this season.
But they will also be flying the flag for a Premier League that has been humbled in Europe this season, with Arsenal the latest English club to endure embarrassment when they were thrashed 4-0 by AC Milan on Wednesday night.
But even Arsenal fared better than Manchester United and Manchester City, who both crashed out of the Champions League before Christmas.
That has left Chelsea as England's only realistic challengers for a place in the quarter-finals, something of which captain Terry is acutely aware.
He told Chelsea's official matchday programme: "With Arsenal in a position that is looking hard to turn around, we could end up being the only English team left in the Champions League and it is really important to make a good start to the tie."
Terry is keeping his fingers crossed he will return to lead Chelsea out on Tuesday, having missed the last three weeks with a knee problem.
"I've been struggling with my knee recently but, hopefully, I will be back in some capacity," he added.
But manager Andre Villas-Boas told ESPN today: "There is a 50-50 chance of him making it.
"He's going to train on Monday and travel with the team. After that, we'll make a decision."
Chelsea have missed Terry badly recently, failing to win any of their matches in his absence, including today's FA Cup fifth-round victory over Birmingham.
Their drop to fifth in the Premier League led to even more speculation about the future of Villas-Boas and today's result piled on the pressure.
That will multiply if he fails to mastermind victory over Napoli, who have been one of the surprise packages of this season's Champions League.
Their Serie A form has been patchy but that did not stop Walter Mazzarri's men humbling Manchester City at the Stadio San Paolo.
Branislav Ivanovic is under no illusions about the task facing Chelsea.
The defender said: "We're expecting one of the hardest games of our season - it's away in Europe, playing at a stadium where it's very difficult to play.
"We know all these things and we have to prepare for this.
"But it's good that we play the first leg away and it will be a new experience for us."
A positive result would be the perfect early birthday present for Ivanovic, who turns 28 on Wednesday.
"After 20, I stopped counting - is it really 28 now?" he said.
"Maybe the statistics say it's the best time for a footballer - you're still young, but you also have experience.
"But I think every player can always improve - his age doesn't mean a lot.
"I will just try to do the same things and keep pushing myself."
Villas-Boas will be keeping his fingers crossed left-back Ashley Cole recovers from a calf problem, while he will also make changes for a game which comes three days after today's cup tie.
Villas-Boas said: "It's a reality that seven months into the season, we will need to be very, very careful with the short time in between the two games.
"Bearing in mind the importance that the trophies have for our season, there's not a lot of playing that you can do.
"Also, we had our injuries recently, a lot of players still coming back, players like we want to introduce in the team.
"We have to be careful with the Napoli game.
"I think, for sure, it will have an impact on selection."
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