The Gunners have lost in both finals that they've been in to date, against Barcelona back in 2006, and on penalties against Paris Saint-Germain in 2026.
They face the Partenopei on the back of a great start to their Premier League season, which has seen them win all three games played, and they've only been kept off top spot by virtue of the fact that Man City have scored one more goal.
Arsenal have won three of the last four vs Napoli
It's the first time that the two teams have met in the competition since 2018/19, and in the previous four encounters, Arsenal have won three and kept clean sheets in all of those victories.
With the Gunners having only conceded one goal so far this season, and only being behind in last season's Champions League for 42 minutes and 48 seconds (not having lost in normal time throughout), the size of the task awaiting Napoli is obvious.
That said, the North Londoners have only won one of their last six away trips on Italian soil in the UCL (D1, L4), and haven't scored in five of those matches.
Napoli have lost only three of 13 home ties against English opposition
The hosts have lost just three of 13 home ties against English opposition in major European competitions (W8, D2), but haven't been in the best form at the start of this season, winning only one Serie A game, scoring five goals but conceding five also.
Arsenal's solitary win from their last six UCL games in Italy came in January of this year at Inter, whilst Napoli did lose in the first month of 2026 to Chelsea; however, in 37 UCL/European Cup ties at home, the Partnopei have never lost two matches in succession.
In Kevin De Bruyne, they have a player who knows how to unlock a notoriously tight Gunners defence, too.
The Belgian has been involved in 12 goals (8G, 4A) in his last 17 appearances against the North Londoners in all competitions, and he, perhaps more than anyone, is likely to test David Raya's record of having kept a clean sheet in 53% of his Champions League starts (19 from 36 games).
Raya and Gabriel are key for the Gunners
That's the highest percentage of clean sheets of any goalkeeper in the competition who's made at least 25 starts, and his form between the sticks went a long way to Arsenal only conceding seven goals in their 2025/26 UCL campaign.
In order to even get close to Raya, Napoli's attackers have to get the better of Gabriel Magalhaes, and that's no easy task.
The Brazilian has won 82 of 121 one-on-one duels attempted in the UCL since the beginning of the 2024/25 campaign.
That 68% success rating is the highest of all 174 players to attempt at least 100 duels during that time, and even without William Saliba alongside him, Gabriel remains the fiercest of competitors.
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Poor current form for the Partenopei
Even further up the field, Bruno Guimaraes has a chance to show Gunners supporters what he's all about, assuming he is selected by Mikel Arteta.
With 2.2 defensive line-breaking passes per game for Newcastle in the competition last season, his output was better than any other player who had played at least 300 minutes.
Rasmus Hojlund will revel in the opportunity to get one over on a rival from his Man Utd days, but Napoli have to do better collectively than they managed at Inter during the weekend.
From a 2-0 lead after 53 minutes, which included a goal from Hojlund, the visitors somehow contrived to lose 3-2, and that's not the best way for Max Allegri's team to be approaching this match.
Though any result in the opening game of a Champions League campaign isn't necessarily disastrous for either side, it does set the tone, and the confidence gained from earning three points can't be overlooked.
It promises to be an absorbing game of football, with both sides in with a genuine chance of getting a positive result.