In 1965, Altafini joined Napoli, due to his disagreements with Amarildo and Paolo Ferrario at Milan, where he formed a notable attacking partnership with Italo-Argentine advanced playmaker Omar Sivori, who had been his Italy teammate at the 1962 World Cup in Chile. He remained at the club for seven years, until 1972. On 31 December 1967, in a 2–2 home draw against Torino, Altafini scored an acrobatic goal from a bicycle kick, a "golaço" which made him extremely popular with the Napoli fans. During his time at the club, he helped Napoli to compete for the title regularly, and he was able to lead Napoli to their best ever Serie A finish up until that point, helping them to finish second in the 1967–68 Serie A campaign, behind his former club Milan, also finishing as the second highest goalscorer in Serie A that season. He also helped them finish in third place in 1966 and 1971. During the 1971–72 season, Altafini also helped Napoli to the 1971–72 Coppa Italia final, although they were defeated 2–0 by his previous club, Milan. Despite his role in the club's history, during his time at Napoli, Altafini only managed to win a minor trophy, the Coppa delle Alpi, during the 1966–67 season.