The Bundesliga club upset the odds to reach the Wembley showdown in May, overcoming Real Madrid in the semi-final before seeing their dreams of glory shattered by German rivals Bayern Munich.
Jurgen Klopp's side also finished runners-up to Bayern domestically, but despite losing key player Mario Gotze to their rivals, many consider Dortmund to possess a significantly stronger squad this term.
The arrivals of Henrik Mkhitaryan, Pierre-Emerick Aubameyang and Sokratis Papastathopoulos have helped them reel off five league wins on the bounce at the start of the campaign.
But they travel to Naples on Wednesday with a relatively poor record against Italian opposition.
From their 27 matches, they have won nine and lost 14, and although Napoli were defeated in each of their two previous home matches in Europe, Rafael Benitez's side have not suffered a Serie A loss at the Stadio San Paolo in 2013, winning 10 of their 12 fixtures.
The visitors warmed up for their journey to Italy with a brilliant 6-2 win over Hamburg and Marco Reus, who grabbed their fifth, is feeling positive about the team's prospects.
He told the Bundesliga's official website: "We didn't give up at 2-2 and demanded more of ourselves, now we focus on the Champions League.
"More intensity like that over a full 90 minutes and we'll be difficult to beat. I've got my rhythm and confidence back. All I care about is football, I love it, and I love this team. Now on to Napoli."
Like their opponents on Wednesday, Napoli also had the misfortune of seeing their star player depart in the close-season as Edinson Cavani joined Paris Saint-Germain.
However, with the help of the Uruguayan's €64.5 million price tag, they were able to bring in a plethora of reinforcements, including Real Madrid trio Gonzalo Higuain, Jose Callejon and Raul Albiol, as well as Dries Mertens, Pablo Armero and Duvan Zapata.
Benitez's men go into their opener full of confidence after picking up a maximum nine points from their opening three matches, with their most recent outing seeing them comfortably dispose of Atalanta at home.
The Spanish boss has history in this competition, having led Premier League club Liverpool to the crown against the odds in 2005.
