The sides sat top of the Premier League and Serie A will meet on Tuesday when Napoli travel to Arsenal in the UEFA Champions League.
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.
|Coach: A. Wenger|
for T. Rosický 63'
for A. Ramsey 88'
|Eredvisie Review: Vitesse denied by late Uth goal, NAC Breda boost survival hopes|
|Rangers 1 Motherwell 3: McCall´s men facing uphill struggle|
|Hamburg 1 Karlsruher 1: Bundesliga side escape with draw|
|Blatter vows to lead FIFA clear of trouble as corruption scandal rolls on|
|Bundesliga: Bayern Munich season review - League crown not enough to signal successful campaign|
|Genoa forced to wait for UEFA licence|
|Injured Cardozo out of Paraguay squad|
|CONCACAF provisionally dismisses Webb and Li|
|Klopp: Career highlights of a charismatic coach|
|Verona v Juventus: Ogbonna seeks strong Champions League warm-up|
|FA charges Demetriou over betting breaches|
|Atalanta v Milan: Inzaghi faces last chance to prove worth|
|King joins Bournemouth as QPR rebuild begins|
|Plymouth part ways with Sheridan|
|Hernandez banned for three matches|
|Chelsea star Fabregas has nose surgery|
|Blatter: More bad news may follow|
|Galliani hopeful over Ancelotti deal|
|Frontzeck to continue as Hannover coach|
|Tremmel released as Tate waves goodbye to Swansea|
|Arsenal v Aston Villa: Sherwood out to upset holders|
|UEFA open to boycott of World Cup - Platini|
|Porto activate release clause for Casemiro|
|Athletic Bilbao v Barcelona: Catalans seeking second leg of treble|
|Auxerre v Paris Saint-Germain: History beckons for Ligue 1 champions|
|Cole confirms West Ham departure|
|UEFA elect not to boycott FIFA Congress|
|Borussia Dortmund v Wolfsburg: Klopp aiming for triumphant farewell|
|Flamini hails Coquelin impact at Arsenal|
|South Africa deny wrongdoing in World Cup bid|
|Benitez confirms Napoli exit|
|McShane among six released by Hull|
|Cerci committed to Milan|
|West Ham expect Collins to return for pre-season|
|Real deny Pogba bid|
|Important to keep Chelsea squad together - Mourinho|
|Alonso: Gerrard was magic|
|Pochettino silent on Ings speculation|
|Visa threatens to ´reassess´ sponsorship amid FIFA scandal|
|Blatter skips FIFA Medical Conference|
|MLS Preview: Revs not out for revenge against Galaxy|
|MLS Review: Sounders go top in West, Timbers and Galaxy win|
|AFC stands by Blatter|
|Matheus ´alright´ after collapse - Markevych|
|Copa Libertadores Review: River, Inter through to semis|
|Signing Toni a ´long shot´ for Adelaide|
|Ramsey good enough for Barca - Coleman|
|Bacuna pushing for Benteke stay|
|Evans stunner settles City friendly in Toronto|
|Banega: Emery a great coach|
|Emery tight-lipped on Sevilla future|
|Argentina finalise Copa America squad|
|Nike issues statement following arrest of FIFA officials|
|Hero Bacca grateful for Europa League triumph|
|Markevych rues defensive errors in Dnipro defeat|
|AFC Champions League Review: Naft Tehran fairytale continues|
|Emery: We deserved Europa League success|
|Dnipro 2 Sevilla 3: Bacca brace sees holders make history|
|South Africa 0 Malawi 0 (4-5 on penalties): Harawa heroics send Bafana Bafana out|
|CONCACAF and CONMEBOL respond to arrests in FIFA scandal|
|FIFA president Blatter welcomes investigations as corruption probe rocks world football|
|UEFA calls for FIFA elections to be postponed|
|BREAKING NEWS: Advocaat exits Sunderland and retires from club management|
|La Liga: Real Madrid season review - Ancelotti pays the price for disappointing season|
|Zambia 3 Ghana 0: First-half spree does the damage|
|Barnes suffers double knee ligament injury|
|Balotelli to stay at Liverpool - agent|
|Kane at the double in friendly win|
|Norwich make Dorrans switch permanent|
|Ings unsure of next move|
|Bournemouth snap up Federici|
|FIFA ´crisis´ cannot continue - Prince Ali|
|Barton headlines QPR exits|
|Juan demands more from Inter|
|Stoke snap up Haugaard|
|Subotic commits to Dortmund|
|Warner pleads innocence after US indictment|
|Napoli to refuse questions on Benitez´s future|
|USDoJ names indicted FIFA officials|
|Wenger coy over Vidal and Benzema moves|
|Suarez back in training ahead of Copa final|
|Pique: I´ll retire at Barca|
|Gerrard ´blown away´ by Liverpool send-off|
|FIFA ´very happy´ with Zurich arrests|
|Liverpool defender Toure targeting trophies|
|Ramsey eyeing title assault|
|Welbeck out of FA Cup final and England matches|
|FIFA the ´injured party´ as Swiss prosecutors open criminal proceedings|
|Prince Ali saddened by FIFA arrests|
|Pellegrini to make City defence a priority|
|Labbadia giving Lasogga, Olic, Jiracek time|
|Ramsey confident on Wembley chances|
|Swiss authorities confirm FIFA arrests|
|El Shaarawy open to Premier League move - agent|
|Reports: FIFA officials set to be arrested|
|Tigres UANL 2 Emelec 0 (2-1 agg): Mexicans through to Libertadores semis|
|Valencia ruled out of Copa America|
|Coleman: Bale being ignored by Real team-mates|
|Ruddy eyes England recall|
|Benteke will strike fear into Arsenal - Westwood|
|Howe named LMA Manager of the Year|
|Casillas reiterates desire to stay in Madrid|
|Dnipro players pay for fans´ tickets, transport|
|Galliani: I want Ancelotti back at Milan|