Klopp's men visit the Stadio San Paolo for the first game of their 2013-14 UEFA Champions League campaign, after narrowly losing out to Bayern Munich in last season's final.
Dortmund will naturally be looking to go one better this campaign, but face a tough assignment in a group that also contains Premier League side Arsenal and French club Marseille.
Napoli underwent a close-season overhaul under new manager Rafael Benitez, bringing in the likes of Gonzalo Higuain, Dries Mertens and Jose Callejon while losing star striker Edinson Cavani to Paris Saint-Germain.
Klopp is aware of the danger posed by Benitez's side, and is anticipating an exciting encounter.
"Napoli play a very lively kind of football, it's not too different from ours," he said.
"If you look at the players at Napoli, they have a very experienced defence while their attack stands for pace and technique.
"We do not fear them, but we know what we are dealing with and have a lot of respect."
