Victories against Cesena and AC Milan have seen Napoli join Juventus, Udinese and Cagliari at the top of the Serie A standings.
"It's a nice feeling," Napoli defender Paolo Cannavaro said. "We certainly could not have asked for a better start."
Napoli won 3-1 against defending champions AC Milan on Sunday but coach Walter Mazzarri was not impressed by his team's performance in that game.
"I know we got a good result against Milan," he said. "We did nice things but considering how I want my team to play, we have to do better.
"We must continue to improve.
"We didn't have much possession against Milan and we need to show more personality on the pitch."
Mazzarri will have all of his players available for Wednesday's match with the exception of Uruguay midfielder Walter Gargano, who is sidelined through injury.
While Napoli have enjoyed an impressive start to the campaign, that has not been the case for Chievo, who have yet to claim a win.
Under new coach Domenico Di Carlo, the Flying Donkeys were held to a 2-2 draw by Novara before falling 2-1 at Parma last time out.
Despite their poor start, Di Carlo believes his team can kickstart their season against mighty Napoli.
"We struggled to get results in our last two games but we put in two good performances," he said. "I am optimistic that we can get a positive result against Napoli."
Chievo fans have reason to be confident for their side beat Napoli 2-0 earlier this year having previously won 3-1 in Naples.
The hosts will be without captain Sergio Pellissier, who is out with a thigh injury.