A cable broke on the cableway linking the town of Castellammare di Stabia, in the Gulf of Naples, to Mount Faito – about three kilometres away – shortly after 3pm.
Witnesses on the ground said that the cable car plummeted into the valley below, hitting a pylon and a construction site on the way down, according to Italian media reports.
"Four bodies were found, while a fifth injured person was rescued and taken to hospital," Italy's fire department said, adding that this was the final toll.
Two British nationals were among the victims of the accident.
They were identified as Margaret Elaine Winn, 58, and Graeme Derek Winn, 65, according to Italian news agency Ansa.
The UK Foreign Office is "supporting the families of a British couple who have died in Italy and are in touch with the local authorities,” a spokesperson said, according to British media reports.
The other victims were Italian cable car operator Carmine Parlato, 59, and Janan Suliman, a 25-year-old Israeli woman.
Suliman's brother, Thaeb, 23, was reported as being in critical condition at a Naples hospital after suffering severe injuries in the crash.
Over 50 firefighters took part in rescue efforts.
Sixteen passengers were helped out of a separate cable car that was stuck mid-air near the foot of the mountain.
They were rescued one by one in a difficult operation that was hampered by fog and winds reaching 100 km/h, according to local reports.
The cable car accident took place just over a week after the link reopened for the summer season.
"The cableway reopened 10 days ago with all the required safety conditions," said Umberto de Gregorio, head of the EAV public transport company, which runs the service.
"What happened today is an unimaginable, unforeseeable tragedy," he added.
The Torre Annunziata Public Prosecutor's office has launched an investigation into the accident, Il Corriere della Sera reported.
The mayor of Castellammare di Stabia, Luigi Vicinanza, said late on Thursday that the cable car's emergency braking system may have malfunctioned after the "traction cable snapped".
Prime Minister Giorgia Meloni expressed "sincere condolences" to the families of the victims, her office said late on Thursday.
Culture Minister Alessandro Giuli also expressed his condolences to the victims on Friday, saying: “Our most sincere thoughts go to the community affected and to all those who are facing the consequences of this tragedy.”
“Monte Faito is a symbolic place. As a guardian of natural beauty, to see it today as the scene of such a tragedy saddens us deeply," he added.
The cable car service running between Castellammare di Stabia and Mount Faito has been operating since 1952.
Four passengers, including a nine-year-old child, were killed in a similar accident in 1960.
Thursday's accident came less than four years after a cable car crashed in the Italian Alps near Lake Maggiore, killing 14 people.
With reporting from AFP.
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