The contest is a repeat of last season's Coppa Italia semi-final - which Napoli won 5-3 on aggregate - with Benitez's resurgent charges eager to put a dent in Roma's title challenge and kickstart their own this weekend.
Rudi Garcia's side are behind Serie A champions Juventus on head-to-head record alone, but will move top - albeit possibly for just a few hours - if they avoid defeat.
Juventus make the trip to Empoli later in the day - looking to bounce back from their defeat to Genoa last time out - and Benitez wants Napoli to exhibit the form that saw them beat Roma in their last two meetings.
"[The] game is an opportunity to show our ambitions once again," the Spaniard said.
"We have seen that every team can drop points so we are aware that if we win we can close the gap [to Juventus and Roma].
"With the top teams we have always raised our level and this year it should be the same.
"We have seen both against Atalanta and Chievo that we managed to create many chances and we were controlling the game."
Roma could occupy top spot by the time Juve take to the field at the Stadio Carlo Castellani, although Massimiliano Allegri's side will be heavy favourites to return to winning ways against strugglers Empoli.
Lazio missed the chance to cut the defecit to rivals Roma in midweek as they were held to a 1-1 draw by Verona and they may fall further off the pace before hosting Cagliari on Monday.
Milan, Sampdoria and Udinese - the three other sides on 16 points - are all at home this weekend as they take on Palermo, Fiorentina and Genoa respectively.
Inter's visit to the Stadio Ennio Tardini could prove critical for Parma coach Roberto Donadoni, whose position is reportedly under pressure after a dismal start to the campaign.
A return of three points from nine games this term has led to reports ex-Italy boss Donadoni may be replaced by youth team coach and legendary former striker Hernan Crespo.
Fellow strugglers Chievo and Cesena host Sassuolo and Verona respectively with the league's bottom two having won just twice between them all season in the top flight.
Atalanta - who have taken just four points from their previous possible 15 - take on Torino at the Stadio Olimpico di Torino.
