The clubs lie third and second respectively, separated only by goal difference, and are just three points adrift of the league's standout performers so far this season.
Both have kept up the pressure on Roma in recent weeks and will have spotted a chance to pounce, with Rudi Garcia's men having dropped points for the first time this term in a 1-1 draw with Torino last time out.
Juve picked up a 1-0 victory at Parma last weekend before battling to a 2-2 draw with Real Madrid in the UEFA Champions League. Napoli took part in their own continental thriller on Wednesday as they ran out 3-2 victors over Marseille, having beaten Catania 2-1 last Saturday in domestic action.
The hosts won this clash 2-0 last season and victory for either side this time around could see them pull level on points with Roma in the unlikely event they lose to lowly Sassuolo.
Despite their minor slip-up last weekend, the league leaders will be confident of picking up maximum points at home against the 18th-placed outfit, who have just two victories to their name so far, although they did beat Sampdoria 4-3 in their most recent match.
This will be the first encounter between the sides following the visitors' promotion to Serie A last season.
Elsewhere in the Italian top flight, Inter aim to keep pace with the leading pack as they take on Livorno at San Siro on Saturday.
Walter Mazzarri's men, for whom Javier Zanetti could return from injury, sit fourth, six points adrift of Napoli and Juventus, but have only taken two victories from their last six league fixtures.
In Saturday's only other tie, Catania will be hoping to bring their five-game winless streak to an end when they host Udinese at Stadio Angelo Massimino.
As well as the top-of-the-table tussle, Sunday will also see Milan trying to break themselves out of a run of three matches without a win.
Manager Massimiliano Allegri is under increasing pressure to produce results with his side lying 11th and could find his job in more danger should they lose to bottom-placed Chievo.
Verona and Fiorentina join Inter in chasing down the top three as they take on Genoa and Sampdaria respectively, while Sunday's remaining ties see Parma host Lazio, Bologna travel to Atalanta and Cagliari face Torino.
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