Both secured 2-1 wins in the opening round of matches and will square off in competitive action for the first time at the Emirates Stadium.
Arsenal are on a nine-game winning run in all competitions, with defeat to Aston Villa on the opening day of the Premier League season the last time the London club tasted defeat.
Their latest success came in Saturday's 2-1 victory away to Swansea City, with a first professional goal from Serge Gnabry and an effort from in-form Aaron Ramsey - his fifth in his last four games - proving enough for the points.
And manager Arsene Wenger is confident that three points against the Serie A side will leave them in a strong position to reach the round of 16.
"If we win the second game we know we can qualify," he said.
"I wouldn't say it is already a decisive game - but it is a game that will have a great bearing on who qualifies.
"If we deal with that situation then we will be in a very positive mood to finish the job."
Arsenal's form has been all the more impressive with an injury list that includes Lukas Podolski (hamstring), Santi Cazorla (ankle) and Theo Walcott (stomach) among the players on the sidelines.
But defeating Napoli will be no easy task, as Rafael Benitez's tenure at the Stadio San Paolo has started in terrific fashion.
Napoli have won five and drawn one of their six Serie A fixtures, and began their Champions League campaign with an impressive triumph over last season's runners-up, Borussia Dortmund.
Goals from Gonzalo Higuain and Lorenzo Insigne did the damage on that occasion, and they claimed the maximum haul despite Camilo Zuniga's late own-goal.
Despite their excellent start, Benitez believes the side is yet to reach their full potential, but says the club are confident of their chances in London.
"We talk with the team every day and we know that we are at 75 per cent," he told the club's official website.
"Now we must continue to grow. I know that we can and we must be competitive to try and win against all opponents.
"That is what we will try to do in London against Arsenal."
Christian Maggio (knee) is Benitez's only absentee, with Higuain set to start against a club he came close to joining over the close-season.
Reports suggested that Arsenal were ultimately unwilling to match
Napoli's fee for the former Real Madrid man, paving the way for a move
to Serie A, while the Argentinian was afforded a frosty reception when
the Naples club played against Arsenal in pre-season during the Emirates
Cup.
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