The azzurri go into the encounter at the San Paolo stadium needing to overturn a 3-2 deficit in the opening semi-final leg.
Benitez's men bounced back from that reverse with a convincing 3-1 Serie A triumph over AC Milan on Saturday.
The outcome lifted Napoli to third place in Serie A, four points behind Roma, who are second and have a game in hand.
"We need a good performance against them," Benitez said in Tuesday's press conference. "Both in the league and in the Coppa, we have played well against Roma and I think the fact that we are playing at home can make a difference."
Napoli have lost just once this season in Naples and Benitez is confident his players can deliver come Wednesday.
"The Coppa Italia is an important competition for us and I would like to win it even though it will not be easy," Benitez said. "We will put out the strongest team.
"Fortunately, I have all my players available and in good condition.
"(Argentinian striker Gonzalo) Higuain has the quality to change a game but I have confidence in all of my players."
Napoli midfielders Jorginho and Gokhan Inler as well as striker Jose Maria Callejon are expected to start against Roma with the trio suspended for Sunday's game at Sassuolo.
Roma coach Rudi Garcia expects a battle from start to finish in Naples.
"Napoli have to win and we will go there determined to gain qualification," he said. "Our philosophy is to play attacking football and we will go out there determined to win.
"Napoli have had one more day to prepare this game but we are charged up."
The Giallorossi were runners-up in the competition last season behind city rivals Lazio and are eager to lift their 10th Coppa trophy this season, their first since the 2007-08 campaign.
Garcia has received good news with midfielder Miralem Pjanic and defenders Mehdi Benatia and Douglas Maicon all fit to play.
All three players suffered muscular problems during Sunday's goalless result against Lazio in the Eternal City derby.
The visitors are without midfielder Radja Nainggolan, who serves a one-match ban.
The victors will face the winner of Tuesday's semi-final between Fiorentina and Udinese.