With the first silverware of the season at stake, the Serie A champions take on last season's Coppa Italia winners - a repeat of June's dramatic cup final in Rome.
While Italy's most decorated club, Juventus, have claimed the Supercoppa trophy eight times since it was first awarded in 1988 (in 1995, 1997, 2002, 2003, 2012, 2013, 2015 and 2018), Napoli have done so just twice - beating the Bianconeri on both occasions (1990 and 2014).
This time, Andrea Pirlo's outfit approach potentially one of the most explosive games of the season on the back of a devastating Derby d'Italia defeat to fellow Scudetto contenders Inter Milan on Sunday.
Champions for nine seasons running, Juve had been making up ground lost due to a succession of draws in the autumn by winning their first three fixtures of 2021, including their last trip to San Siro - a convincing 3-1 success against Milan.
Victory on Sunday would have taken Pirlo's men one point behind Inter with a game in hand - to be played versus Napoli at a yet to be determined date - but they were picked off at will by Antonio Conte's ruthless counter-attacking unit.
Questions remain, then, about the capabilities of their rookie coach and his squad's progression since the playmaking legend took charge in the summer. Certainly, Pirlo's old Bianconeri boss Conte won the tactical battle of 'Master versus Apprentice', as old reliables Giorgio Chiellini and Leonardo Bonucci were constantly caught out in Milan.
That momentum-shattering defeat leaves Juventus fifth in the Serie A standings - one point and two places behind Wednesday's super-motivated Supercoppa opponents.
This week, Napoli meet their old northern foes on neutral territory - at the home of serial overachievers Sassuolo, in Reggio Emilia. With three wins from three since their awful collapse against ten-man Spezia at the start of the month, the Partenopei will travel to the compact Mapei Stadium full of confidence.
Captain Lorenzo Insigne netted a brace in the 6-0 destruction of Fiorentina at the weekend - which moved his side third in the table - and will again lead the Naples giants into battle in search of a second straight triumph over the Old Lady of Turin.
The last time the clubs met was in the Coppa Italia final at the climax of a tumultuous 2019-20 campaign, when Napoli prevailed on penalties after a tense goalless draw. That victory was their fourth meeting with Juventus in finals, each of which they have emerged from the winner - the others were two previous Supercoppa Italiana encounters and the Coppa final in 2012.
Back in October, the season's first scheduled meeting between the pair was controversially cancelled at short notice after Napoli failed to turn up when their entire squad was placed in quarantine by Neapolitan health authorities.
Gennaro Gattuso's team did not travel to Turin after two positive COVID-19 tests caused officials to act and they were initially handed a 3-0 loss by Serie A. Having since won a reprieve after their third appeal against the decision, the 'result' was voided by CONI (the Italian Olympic Committee) and a penalty point revoked.
Bad blood arising from this matter was only exacerbated when the CEO of Serie A, Luigi De Siervo, had to strike out a "provocative" suggestion from colourful Napoli president Aurelio De Laurentiis to also postpone the Supercoppa until the spring, when fans might be able to attend.
For opponents who share a quarrelsome past that reached an unsavoury crescendo during the days of Diego Maradona's reign in Naples, these are just the latest chapters in a deep-held rivalry - one which is set to finally resume on the pitch this week.
Juventus form (all competitions): LWWWWL
Napoli form (all competitions): DWLWWW
How Andrea Pirlo shuffles his pack - if much at all - will be telling, in the wake of their setback at the weekend. In particular, the four-man defence composed of Danilo, Giorgio Chiellini, Leonardo Bonucci and Gianluca Frabotta could be reformulated, particularly with Juan Cuadrado now returning from self-isolation.
There are several spots up for grabs in midfield, with Arthur and Adrien Rabiot, Aaron Ramsey and Weston McKennie plus Federico Chiesa and Dejan Kulusevski all competing against each other for a start.
Napoli's influential midfielder Fabian Ruiz and centre-forward Victor Osimhen are absent due to COVID-19, but back-up striker Andrea Petagna has recovered from a calf problem and should provide the front-line focal point for Gennaro Gattuso's team.
Dries Mertens is not expected to be fit to start against the Bianconeri, but should at least feature from the bench. Skipper Lorenzo Insigne, Piotr Zielinski and Hirving Lozano are in fine form as the trio supporting the front man and should again combine forces in the creative department.
Juventus possible starting lineup:
Szczesny; Danilo, Demiral, Bonucci, Frabotta; Bernardeschi, Arthur, Bentancur, Chiesa; Morata, Ronaldo
Napoli possible starting lineup:
Ospina; Di Lorenzo, Manolas, Koulibaly, Rui; Bakayoko, Demme; Lozano, Zielinski, Insigne; Petagna
We say: Juventus 2-1 Napoli
Juventus can finally get one over on Napoli for the first time in five final attempts, by bouncing back from a disappointingly disjointed display to prove their mettle.
Though this much-anticipated Supercoppa clash could conceivably go either way, Napoli may find Juve just too difficult to stop - certainly if the Bianconeri's experienced strikers are back on song.