Police believe the pair sent weapons including assault rifles, surface-to-air missiles and even helicopters to Iran and Libya between 2011 and 2015, despite an embargo. The couple in their 60's have been named as Annamaria Fontana and Mario Di Leva - known as Jafaar since their conversion to Islam, according to local paper Napoli Today.
Their son and the CEO of the Italian Helicopters Society were also reportedly arrested in connection with the weapons trafficking.
Fontana was well-known locally as a politician, having served two terms as a socialist councillor in San Giorgio a Cremano, Campania, in the 80's and 90's.
In recent years she had moved away from politics and begun to visit the Middle East regularly with her husband, Il Corriere del Mezzogiorno reported, building up close ties with the Libyan government and meeting Iran's former premier.
The arrests were made following a nationwide operation coordinated by Italy's anti-mafia police department in Naple. Police had launched the investigation in 2011, following leads from an investigation into the Camorra mafia clan.