The sides will square off in Naples with Inter sitting in eighth place in the Italian top-flight standings, one place but four points behind Napoli.
However, the Nerazzurri will enter the contest on a decent run of form, having taken 10 points from their last five matches.
The Partenopei have claimed eight points from a possible 15 and it has all the makings of a tight encounter on Friday evening, but Pioli has made it clear his men will not take a backward step against their rivals.
"We have done well so far and through our daily work I believe we can improve even more," he said. "We certainly have no fear about the match tomorrow because each game has its own dangers. We have big personalities in this team and that’s important."