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'
|Everton waiting on Baines fitness|
|I am not under pressure, Pellegrini insists|
|Guardiola demands focus ahead of Braunschweig clash|
|Van Gaal: Di Maria needs a year to settle|
|Luis Enrique vows to attack Villarreal|
|Jedinak hit with four-game ban|
|Mourinho guarantees Terry deal|
|Mowbray lands Coventry job|
|Strootman on schedule for Roma return|
|Mikel out for a month after surgery|
|Palace midfielder Jedinak accepts FA charge|
|Wigan chairman Whelan stands down, hands reins to 23-year-old grandson|
|Jedinak stays quiet on FA charge|
|England winger Johnson released on bail|
|Gareca signs four-year Peru deal|
|Sandro set for QPR return|
|Hull dealt Brady blow|
|Garcia going nowhere, insists Pallotta|
|Allardyce: Chelsea aren´t allowed to be off form|
|Arsenal boosted by Ramsey return|
|No early Barca return for Tello|
|Pirlo inspired stunning Tevez free-kick|
|Brunt vows to heap misery on Villa|
|Barry: Everton needs points on the board to avoid relegation scrap|
|Janmaat hails ´fantastic´ Van Gaal|
|Cahill vows to silence critics|
|Spurs legend Mackay passes away|
|Adrian: I get good results against Mourinho|
|Hoffenheim boss wary of rising expectations|
|Sturridge edging closer to his best - Rodgers|
|Kroos happy with deeper role|
|Terry ´fighting´ for Chelsea contract|
|Townsend: No excuses for Tottenham|
|Garcia applauds Roma´s ´magnificent´ comeback|
|Belenenses 0 Pacos de Ferreira 1: Moreira seals rare away win|
|Juve angry at Roma draw - Allegri|
|Roma 1 Juventus 1: Keita keeps slim Scudetto hopes alive|
|Celta Vigo 1 Elche 1: Controversial late penalty gives visitors a point|
|Turkish Super Lig Review: Gala extend lead at the top|
|Paris Saint-Germain v Monaco: Jardim rejects de-facto final talk|
|Stuttgart, Freiburg named in doping claims|
|Dyche hails Ings determination ahead of Liverpool showdown|
|Newcastle United v Manchester United: Mata out to make more memories|
|England winger Johnson suspended after arrest on underage sex charge|
|Liverpool back in the black|
|Jedinak charged with violent conduct|
|BREAKING NEWS: Police make arrest on underage sex charge amid reports England international is held|
|Schone delighted to extend Ajax deal|
|Montolivo and De Jong suffer injuries|
|Bayern Munich v Eintracht Braunschweig: ´Self-critical´ holders in no mood to ease off, says Muller|
|Tottenham v Swansea City: Pochettino out to banish League Cup disappointment|
|QPR v Arsenal: Austin ready for survival fight|
|Sherwood: No hard feelings over missing out on West Brom job|
|Chelsea and Everton fined for fracas|
|Villarreal v Barcelona: Final in sight for visitors|
|Stoke City v Everton: Howard calls for back-to-basics approach|
|Pearson: I understand Pellegrini pressures|
|West Brom sweating on fitness of Berahino and Ideye|
|Manchester City v Leicester City: Pellegrini demands response|
|Feyenoord and Roma face UEFA charges|
|Liverpool v Burnley: Rodgers full of respect for visitors|
|Brown has red card overturned|
|Rodgers heaps praise on Allen|
|Koeman critical of Jedinak elbow|
|Bruce hits back at Hughes over Figueroa challenge|
|Koeman sets 61-point target for Southampton|
|Ibe set to miss a month with knee injury|
|Klopp looking to maintain momentum|
|Bent out for three to four weeks with hamstring injury|
|Schmidt ready for Kaiserslautern clash|
|West Ham v Chelsea: Mourinho turning attention back to the league|
|Barca must not be distracted by Clasico, says Busquets|
|Terry rules out England return|
|De Boer demands more despite PSV win|
|Bony: We have to win every game|
|Subotic rejects Serbia call-up|
|Benitez frustrated at refereeing decisions|
|Real Madrid must learn from Villarreal draw - Marcelo|
|QPR announce losses of £9.8m|
|Rutten to leave Feyenoord|
|First trophy for ´new´ Chelsea - Mourinho|
|Icardi the future of Inter, says Ausilio|
|Patience needed from ´brilliant´ United fans - Rooney|
|Allen hails ´next level´ Coutinho|
|Points over milestones for Cisse|
|Hecking ´furious´ with Wolfsburg defence|
|CONCACAF Champions League Preview: DC United face uphill task to reach semis|
|AFC Champions League Preview: Al Ain enhanced, Wanderers prepare for Evergrande reunion|
|Coupe de France Preview: PSG, Monaco to meet again|
|Crouch happy to silence doubters|
|Blanc questions rivals´ mental strength as PSG gain ground|
|Kane: Fortune favoured Chelsea|
|Ancelotti defends Isco substitution|
|Rooney: Di Maria will come good|
|Stubborn Villarreal impress Real´s Pepe|
|PSG could not ´kill off´ Monaco - Van der Wiel|
|Serie A Review: Napoli suffer defeat at Torino, Lazio lurking|
|Ligue 1 Review: Title chasers´ slip-ups go unpunished|
|La Liga Review: Real and Atletico suffer frustrating draws|
|Primeira Liga Review: Porto´s Tello dents Sporting´s title hopes|
|Monaco 0 PSG 0: Champions miss chance to go top|
|Real Madrid 1 Villarreal 1: Moreno leveller ensures stalemate|
|Simeone satisfied with Sevilla point|
|Henry: Chelsea can win a trophy treble this season|
|Mancini frustrated by ´hesitant´ Inter|
|Sevilla 0 Atletico Madrid 0: Simeone´s men in fiery draw|
|Pochettino upbeat despite League Cup defeat|
|Inter 0 Fiorentina 1: Montella´s men end San Siro wait|
|Bundesliga Review: Wolfsburg edge eight-goal thriller, Monchengladbach win|
|Mourinho revels in ´beautiful´ League Cup success|
|Eredivisie Review: PSV lose home record as Ajax close the gap|
|Terry thrilled by ´massive´ League Cup final win|
|Chelsea 2 Tottenham 0: Mourinho´s men seal League Cup success|
|Coquelin sustains broken nose|
|Wenger hails Giroud character after Everton goal|
|Everton not getting what they deserve - Martinez|
|Coutinho is coming of age at Anfield - Rodgers|
|Football League Preview: Wolves in the hunt for back-to-back promotions|
|Norwich City 2 Ipswich Town 0: Neil´s men go third with derby triumph|
|Southampton v Crystal Palace: Fonte focusing on big picture|
|Arsenal 2 Everton 0: Giroud strikes to silence doubters|
|Dynamo Dresden v Borussia Dortmund: Hummels eager to build on derby win|
|Rodgers tips hat to relentless Liverpool|
|City facing uphill challenge to retain title - Pellegrini|
|Celtic 4 Aberdeen 0: Champions dominate top-of-the-table clash|
|Lallana hails ´massive´ win as Liverpool´s top-four charge continues|
|Hull City v Sunderland: Cattermole allowing no excuses against ´bogey team´|
|Liverpool 2 Manchester City 1: Coutinho dents City´s title hopes|
|Sunderland to appeal Brown red card|
|Aston Villa v West Brom: Sherwood looking for confidence boost|
|Allegri not taking risks on Vidal and Pogba|
|Pardew defends Jedinak over Sakho elbow|
|Heldt apologises after Schalke´s derby humbling|
|Milan must give that bit extra - Bocchetti|
|Rooney: Brown red must be rescinded|
|Monk hails Swansea´s versatility|
|Melbourne Victory 2 Wellington Phoenix 3: Hosts miss chance to go top|
|Rodgers: Top-four finish would be bigger than last season´s effort|
|Batman and Robin ´a bit of fun´ - Reus|
|Rakitic feeling better after ending goal drought|
|Copa Libertadores Preview: Well-rested Cruzeiro ready for Universitario|
|Fournier fuming after Lyon loss|
|DFB Pokal Preview: Gladbach visit rusty Offenbach|
|Mourinho: Tottenham approached me|
|Primeira Liga Review: Birthday boys Benfica hit Estoril for six|