The Ivorian's late strike completed his double and gave his side a slim advantage heading into the second leg.
Gervinho's late winner gave Roma a dramatic 3-2 win over Napoli in the first leg of their Coppa Italia semifinal on Wednesday.
Roma's push for a 10th Coppa Italia title looked to be gathering pace when Gervinho and Kevin Strootman scored in the first half to set Rudi Garcia's men on their way.
Gervinho's clever finish put Roma ahead in the 13th minute and Strootman's stunning strike from distance just after the half-hour mark doubled the lead.
But an own goal from Roma goalkeeper Morgan De Sanctis in the 47th minute brought Napoli back into the contest and it equalized with 20 minutes left thanks to substitute Dries Mertens, who was introduced just four minutes prior for Marek Hamsik.
Gervinho – Roma's top scorer this season – had the last laugh though, scoring with two minutes left to give his side the advantage heading into the return fixture.
Roma's Serie A clash against Parma on Sunday was abandoned after just nine minutes due to a deluge of rain at Stadio Olimpico but the pitch held up on this occasion.
As a result, Roma entered the match fresher than Napoli – which was stunned 3-0 at Atalanta on Sunday – and after a slow start, the hosts found their rhythm.
Gervinho scored from his side's first meaningful attack when he timed his run to perfection following an excellent ball from Francesco Totti.
The ex-Arsenal forward cut inside Anthony Reveillere and avoided Raul Albiol, showing great composure to dink the ball over the onrushing Napoli goalkeeper Pepe Reina before tapping into an empty net.
Napoli then failed to close down Totti and his fierce shot from distance stung the palms of Reina, while Reveillere limped off with an injury, to be replaced by Faouzi Ghoulam.
Roma doubled its lead in stunning fashion, as Strootman took advantage of the free space before lashing a fierce 25-yard left-foot effort into the top corner in the 32nd minute.
Napoli had a penalty appeal turned down on the stroke of halftime as Christian Maggio failed to get a shot away under the attention of Vasilis Torosidis, but the away side did pull a goal back two minutes after the break.
Gonzalo Higuain's attempted cut-back deflected off Mehdi Benatia and was spilled onto the post, and then in, by former Napoli goalkeeper De Sanctis for an unfortunate own goal.
Adem Ljajic then forced Reina to tip behind before shooting wide twice, and the keeper also moved well to keep out a deflected Torosidis effort.
Roma was made to pay for its missed chances as Mertens leveled for Napoli with 20 minutes left.
Higuain had been fouled but the advantage was played, and Mertens skipped past Leandro Castan before lashing beyond De Sanctis with his right foot.
There was still time for more drama though, as Gervinho – who got the winner in the quarterfinal against Juventus - finished a move that involved substitutes Mattia Destro and Alessandro Florenzi with a neat near-post finish.