Rud Garcia's men are chasing a 10th Coppa Italia title but will need to overcome Rafa Benitez's men over two legs, with the first at the Stadio Olimpico on Wednesday
Rudi Garcia's charges have lost just one match in all competitions this season - to Serie A leaders and champions Juventus - giving them cause for confidence as they look to book their place in a second successive final.
The Giallorossi's efficient displays have seen them eliminate Sampdoria and Juve with consecutive 1-0 home victories, while Napoli have dumped out Atalanta and holders Lazio.
The capital-based club last won this competition in 2008, when they picked up a 2-1 victory over Inter in the final, while Napoli's latest success came four years later when they triumphed 2-0 against Juventus in what was their first final appearance since 1997.
Roma's aforementioned strong form sees them occupy second spot in the Italian top flight, nine points behind Juve with a game in hand, and they will be well rested after their fixture against Parma was abandoned due to adverse weather conditions on Sunday.
Third-placed Napoli wasted a chance to close the gap on Roma at the weekend, though, as they suffered a 3-0 defeat at Atalanta.
The hosts last lost at home to Napoli in February 2011, when Edinson Cavani scored two second-half goals to complete a league double over Roma.
Miralem Pjanic found the net twice as Roma claimed a 2-0 victory when the sides met in the league earlier this campaign.
Federico Balzaretti is nearing a return from injury for Roma but is unlikely to feature on Wednesday, while the Partenopei are likely to be without long-term absentees Valon Behrami and Giandomenico Mesto.
New signing Jorginho, who made his debut in last week's quarter-final win over Lazio, will be keen to prove his worth to the team having been omitted from Napoli's Europa League squad.