The home side, who are under new management this season with Rafael Benitez, invested heavily in their squad over the summer as they prepare for just their second campaign in the group stages of the Champions League.
However, Napoli have not beaten German opposition in any of their last seven fixtures, losing five times and drawing twice in the process.
Dortmund, meanwhile, finished runners-up to domestic rivals Bayern Munich in the Champions League last season. Their record against Italian opposition is not particularly strong, however, with 14 defeats from 27 matches.
As mentioned, Napoli will enter the match sitting atop the Serie A table, having won all three of their league fixtures to date and scoring nine times. Dortmund, meanwhile, have won all five of their Bundesliga fixtures thus far, with 15 points leaving them top of the division.
Benitez could recall Jose Callejon to his starting lineup, while Marek Hamsik is also expected to step back into the team at the expense of Giandomenico Mesto. Gonzalo Higuain, Pepe Reina and Raul Albiol are all due to make their Champions League debuts for the Italian club.
Possible starting lineups
Napoli: Reina; Cannavaro, Albiol, Armero; Hamsik, Inler, Mertens, Dzemaili, Insigne; Callejon, Higuain
Dortmund: Weidenfeller; Schmelzer, Hummels, Subotic, Bender; Sahin, Mkhitaryan, Kehl; Reus, Lewandowski, Aubameyang
Sports Mole says: 1-1