Although only the seventh match of the season for both teams, the game is likely to prove a key moment in the title race and Napoli's bid to end the Turin side's run of seven successive scudettos.
Hosts Juventus, who have bolstered their side with the signing of five-times World Player of the Year Cristiano Ronaldo, have won their opening six league games and are in ominous form.
Napoli, in their first season under Carlo Ancelotti, have won five out of six and again look the team with the best chance of ending Juve's dominance.
The dust has barely settled from their meeting in May when Napoli snatched a late 1-0 win in Turin to re-open last season’s title race.
The win prompted wild celebrations in Naples, with around 10,000 supporters gathering at the city’s airport to greet the team's return. But they proved premature and it was Juventus who went on to lift the trophy, prompting pointed comments from defender Giorgio Chiellini.
"Somebody spoke too much and celebrated too early," said the Juve stalwart in remarks which may still be resonating with the Napoli players. "In life, you want respect. And when do you don't show respect, you pay the consequences.
"We were silent when we had to pay and now we can relish the moment deservedly. Never hurt our pride -- that always gives us energy."
Napoli finished as runners-up twice in the last three seasons under Maurizio Sarri.
Most critics agreed that Sarri's team, with their free-flowing football, were the most entertaining side in Serie A but their style was also physically demanding, especially as he was reluctant to rotate and they often seemed to run out of gas.
Ancelotti has inherited the basis of Sarris's side but has not been afraid to tinker, making nine changes to his starting line-up for Wednesday's match against Parma which they won 3-0.
“We met Napoli at the worst time for us,” Parma coach Roberto D'Aversa said. "They have conviction in the ideas of their new coach. Ancelotti has done well everywhere, and he’s trying to transmit his mentality."
Polish striker Arkadiusz Milik, who scored twice against Parma, is one of those players getting more chances under Ancelotti and appears to be flourishing.
"I really like the 4-4-2 system. I’m playing a lot so far this season and it’s good to know the coach has faith in me,” he said.
"We are already focused on Juventus and we can say it’s the game of the season. We’re in good shape and we are going there to win."
(Reporting by Brian Homewood, editing by Ed Osmond)
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