The Blues are back in action in Europe's elite club competition four months after their dramatic penalty shoot-out triumph over Bayern Munich in the German club's Allianz Arena capped a fairytale run under then caretaker boss Di Matteo.
When Di Matteo took charge following Andre Villas-Boas's sacking, it seemed inconceivable that the Italian would finish the season by leading Chelsea to their first Champions League title.
At that point Chelsea trailed 3-1 to Napoli after the first leg of their last 16 tie, but within weeks Di Matteo had inspired a remarkable renaissance that saw the west London club edge past Napoli, Benfica and Barcelona before stunning Bayern in the final.
That was enough to convince Blues owner Roman Abramovich to hand Di Matteo the manager's job on a permanent basis, but the Italian knows it will take a herculean effort to defend the trophy.
No club has won the tournament in back to back years in the Champions League era and, as reigning champions, Di Matteo expects Chelsea to face the very best performances from opponents desperate to claim a big scalp, starting with Italian champions Juventus at Stamford Bridge.
"Every opposition is going to play with extra motivation playing against the holders of the Champions League. So it makes our lives more difficult," Di Matteo said.
"I'm aware no team has defended the trophy and I'm not surprised because it's such a difficult competition to win.
"To win it twice in a row has proven impossible so far, because it's so competitive."
Chelsea's hopes of retaining the Champions League would be greatly improved if Fernando Torres hit the kind of hot streak that Didier Drogba enjoyed towards the end of last season.
Drogba was magnificent during Chelsea's European run, which reached a glorious conclusion with the Côte d'Ivoire striker almost single-handedly dragging his team to the trophy with a late equaliser in the final and then the winner in the penalty shoot-out.
That proved to be Drogba's farewell gift to Chelsea as he moved to China in the close-season and his departure was expected to allow Torres to thrive as the main man.
But another lacklustre display in Saturday's 0-0 draw against QPR, which ended with Torres storming down the tunnel after being substituted, raised more questions about the Spanird's ability to lead the Chelsea attack.
Di Matteo hardly offered a staunch defence of the striker, instead suggesting that England forward Daniel Sturridge could get more playing time.
"We are a team and everybody has responsibility. We're looking for other players to score goals as well," Di Matteo said.
"But we're going to have seven games in 21 days. So there is time for everybody to play.
"Sturridge can maybe play more minutes, for sure. As long as he keeps training well and, when he has the opportunities, shows his qualities, that's the way forward."
Whoever plays up front for Chelsea will find the formidable figure of Juventus keeper Gianluigi Buffon blocking their path to goal.
Juve have been absent from the Champions League for the last two seasons and Buffon (34) is determined to make up for lost time.
"I can't wait to hear the Champions League anthem before kick-off," he said.
"I used to hear it from my sofa, watching the television, during the last few years. I used to think it wasn't fair.
"Now we're back. And Juventus must find that mentality, that ferocity we had last year in winning Serie A to make an impact." – Sapa-AFP