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'
|PSG president confident after Champions League draw|
|Hull closing on Hernandez deal|
|Warnock held Palace talks last year|
|Slomka cools Holtby talk|
|Slomka cools Holtby talk|
|Marotta confident of Juventus success|
|Marotta confident of Juventus success|
|Aguirre: New era for Japanese football|
|CONCACAF Champions League Review: Olimpia go top|
|Torino v Inter: Visitors out to maintain dominance|
|Copa Sudamericana Review: Penarol cruise into second round, Cesar Vallejo do it tough|
|Costa Rican Primera Division Review: Uruguay remain winless|
|Ronaldo backs Di Maria to shine at United|
|Argentine Primera Division Review: Velez stay perfect, Sanchez inspires River|
|Copa do Brasil Review: Cruzeiro win big, Corinthians lose|
|Barca wary of ´difficult´ opponents|
|Ronaldo confident after Champions League draw|
|´Not an easy´ draw for Dortmund|
|Bruce laments ´worst´ elimination|
|UEFA Europa League Play-Off Review: Lyon and Sociedad dumped out, Inter win big|
|Robinson joins QPR|
|Mazzarri lauds Kovacic development|
|Townsend eager to get back to full fitness|
|Tottenham 3 AEL 0 (agg 5-1): Spurs cruise into Europa League proper|
|Leicester complete sensational Cambiasso swoop|
|Del Piero confirms move to Indian Super League|
|Hull City 2 Lokeren 1 (agg 2-2): Lokeren progress despite Brady brace|
|Benatia excited to face Roma|
|Inter 6 Stjarnan 0 (agg 9-0): Kovacic treble sees hosts cruise through|
|Championship Preview: Redfearn in charge for Bolton clash, Magath eyes first league win|
|Newcastle United v Crystal Palace: Warnock kicks off second Palace stint|
|Atletico Madrid v Eibar: Champions seek first win|
|Rodgers excited about ´special´ draw|
|Manchester City v Stoke City: Pellegrini could chop and change|
|Warnock has no issues with Puncheon|
|Sacked Hockaday´s tenure at Leeds lasts just six games|
|Palace re-sign Zaha on loan|
|Burnley v Manchester United: Van Gaal hoping to kickstart recovery|
|Ronaldo named Europe´s best|
|Swansea City v West Brom: Monk wants Liberty fortress|
|Cameroon confident DR Congo clash will go ahead|
|West Ham v Southampton: Koeman anticipating physical West Ham challenge|
|Hughes expecting tough City test|
|Holders Real set for Liverpool test|
|Monk targeting two more additions|
|Koeman keen for ´difficult´ transfer window to end|
|Van Basten absent due to health issues|
|League Two Preview: Morecambe chase another win, giant-killers back in action|
|Irvine eyeing another winger|
|Van Gaal confirms more signings to come|
|Barca are constantly improving, says Rakitic|
|Di Maria is not ´the miracle´, says Van Gaal|
|Torres Milan move ´a real possibility´|
|Juventus v Chievo: Allegri begins quest to replicate Conte success|
|League One Preview: MK Dons and Orient aim to follow up historic wins|
|Schalke v Bayern Munich: Benatia in line for debut|
|Pirlo blow for Juve|
|Napoli defender Ghoulam suffers fractured arm|
|QPR v Sunderland: Redknapp desperate for points|
|Everton v Chelsea: Costa absence could prove costly|
|Deschamps makes two changes to France squad|
|Warnock excited by Palace challenge|
|Lambert: Delph deserves England call-up|
|Aguirre names five uncapped players in Japan squad|
|Ki signs new four-year Swansea deal|
|CSL Preview: Lippi returns to dugout, Beijing Guoan host rock-bottom Harbin Yiteng|
|J.League Preview: Yoshida out to keep pressure on Urawa|
|Chambers, Delph, Colback win England call-ups|
|Rooney named new England captain|
|Costa in doubt for Everton trip|
|Ross County sack Adams|
|Platini wants more UEFA representatives at World Cup|
|Allardyce hints at big-name signing|
|Platini will not challenge Blatter for FIFA presidency|
|Bruce convinced of qualification|
|Alonso set to swap Madrid for Munich|
|Pochettino to use MK Dons as an example|
|Champions League difficult for Arsenal - Bilic|
|Redknapp takes aim at ´really poor´ QPR|
|MLS Preview: Timbers braced for ´massive´ clash in Vancouver|
|Los Angeles Galaxy 4 DC United 1: Arena´s side show quality|
|Copa Sudamericana Review: River Plate, Libertad among teams to progress|
|CONCACAF Champions League Review: Pachuca in seventh heaven, Leon held|
|LDU Quito 3 Deportivo Quito 0: Hosts earn bragging rights against rivals|
|Johnson calm over future|
|Kiessling hails Leverkusen|
|Benitez: Mistakes cost Napoli Champions League spot|
|K. League Preview: Seoul eyeing winning streak|
|Liga MX Preview: Monterrey looking to build momentum|
|Valverde hails ´historic day´ for Bilbao|
|UEFA Champions League Review: Mixed results for Europe´s big guns, Moti the hero for Ludogorets|
|Atletico announce Velazquez capture|
|Giroud set for lengthy absence - Wenger|
|Holders City handed home clash with Wednesday|
|La Liga Preview: Saul not worried by Simeone absence, Barca face tough Villarreal test|
|Eto´o retires from Cameroon duty|
|Aston Villa 0 Leyton Orient 1: Late Vincelot winner sends underdogs through|
|Birmingham City 0 Sunderland 3: Late strikes stun hosts|
|Arsenal 1 Besiktas 0 (1-0 agg): Alexis strike takes Wenger´s men through|
|Stoke City 3 Portsmouth 0: Walters brace sees hosts into League Cup third round|
|Burton Albion 1 QPR 0: Late strike seals upset for fourth-tier hosts|
|Ligue 1 Preview: Bordeaux look to maintain 100 per cent start|
|Dunga: No one guaranteed a place in Brazil squad|
|Serie A Preview: Juve´s Allegri era starts at Chievo|
|Mazzarri calls for professional Inter|
|Utrecht swoop for Peterson|
|Deeney extends Watford stay|
|Alonso calls time on international career|
|Bundesliga Preview: Schalke captain Howedes issues rallying cry, Leverkusen face Hertha|
|Fazio joins Spurs from Sevilla|
|Warnock will control transfers - Parish|
|Pochettino wants Soldado and Townsend to stay at Spurs|
|Augsburg v Borussia Dortmund: Weidenfeller returns for wobbling visitors|
|Celtic complete Wakaso deal|
|Seoul 0 Pohang Steelers 0 (aet, 3-0 on penalties): Yu heroics send Seoul through|
|Guangzhou Evergrande 2 Western Sydney Wanderers 1: Wanderers squeeze through on away goals|
|I´m the future, Benatia´s the past - Manolas|
|Osotspa 3 Chiangrai United 3: Visitors secure point with late rally|
|Israel versus Belgium fixture postponed|
|Fernandes reveals Redknapp contract talks|
|Warnock makes Palace return|
|Eto´o grateful to Mourinho|
|Maiga loaned to Metz|
|Pearson rues ´poor´ Leicester display|
|Bruce: Rhodes deal dead and buried|
|Balotelli set to face Tottenham|
|Di Maria wanted Real stay|
|Dyche wary of inflated transfer market|
|Celtic didn´t deserve Champions League, concedes Deila|
|Game of two halves for Koeman|
|Allardyce hails ´inspired´ Howard|
|CONCACAF Champions League Review: Red Bulls up and running, Rodriguez stars for Saprissa|
|Copa Sudamericana Review: Gimenez double helps Emelec through|
|Eredivisie Preview: Guardado set for PSV bow, Ajax eye recovery|
|Van Gaal ´not shocked´ by Dons defeat|
|Deila: Celtic deserved Champions League exit|
|Barca agree deal for Pereira|
|Lopetegui lauds Porto progression|
|League Cup Review: United hammered by MK Dons, West Ham lose on penalties|
|West Brom 1 Oxford United 1 (aet, 7-6 on penalties): Hosts avoid cup shock|
|Manchester United win ´something dreams are made of´ - Robinson|
|UEFA Champions League Review: Celtic out again, Porto safely through|