The Azzurri are expected to be on the lookout for a new defender in January after Paolo Cannavaro and Gianluca Grava were handed six-month bans for failing to report attempted match-fixing, while veteran full-back Salvatore Aronica is closing in on a move to Palermo.
Rolando, 27, has played a key role for the Portuguese champions since leaving Belenenses in 2008, helping the Dragons to three league titles, three Portuguese Cups and a Europa League trophy.
Quoted in the Corriere dello Sport, Joao Jose Santos Cardoso da Silva told Radio CRC: "He would definitely like to play in Naples.
"Rolando is a smart guy and he knows that Italy has one of the best leagues in the world and that Napoli are a great team.
"If the club and (president Aurelio) De Laurentiis were to make an offer than Rolando would definitely want to play in blue.
"It would take about eight or 10million euros to capture Rolando."
The Cape Verde-born defender is also a full Portugal international and featured in all three of his country's group-stage matches at Euro 2012.