Luigi Esposito, 49, is believed to be one of the heads of the Nuvoletta clan and had been wanted by police since 2003.
In 2006 he was sentenced to nine years in prison for drug trafficking and associating with the mafia and was among Italy’s 30 most wanted men.
Officers arrested Esposito in a residential area of Naples, where he was living under a false name.
Italy’s Interior Minister Roberto Maroni congratulated the police for the arrest.
On Friday Maroni said that 3,600 mafia members, including 15 of the 30 most wanted, had been arrested during the 18 months since Prime Minster Silvio Berlusconi’s govermnent was elected.
Last weekend police arrested three brothers suspected of heading the Russo mafia clan in the Naples area.