The BVB boss has set his sights on avenging the defeat to the Gunners in the 2011-12 group stage, while the team's skipper feels this season's pairings "could have been tougher"
Die Schwarzgelben finished fourth in the 2011-12 group stage after a 1-1 draw and 2-1 loss against Arsene Wenger's men.
However, Klopp is certain his side are now acclimatised to playing at the highest level and are eager to set the record straight against Arsene Wenger's side and fellow Group F opponents Marseille.
"It's a great, evenly-balanced group with four teams that all have what it takes to progress from the group stage," the 46-year-old was quoted as saying on the club's official Facebook page.
"The fact is, we have a score to settle with Arsenal and with [Olympique] Marseille.
"I've never been to Napoli but I'm really looking forward to the atmosphere. It's going to be very exciting."
Hans-Joachim Watzke is also convinced that his side will do better against the two opposing teams this time around.
"Two years ago, we only managed to get one point in total from the games against Arsenal and Marseille and were knocked out at the group stage," the club's president reflected on the 2011-12 campaign.
"Now we have the chance to show our opponents from 2011 how far we have developed."
Meanwhile, midfielder Sebastian Kehl feels BVB will have a tough job in progressing from the group and singled out Napoli as a particularly difficult test.
"It could have been tougher and certainly could have been easier," the team's skipper added.
"We now have the chance to do a much better job against Arsenal and Marseille than we did last time, when we had only just returned to the Champions League after a long absence.
"Napoli was one of the toughest opponents from pot four."