The defender, who spent time with the Partenopei last season, believes Rafa Benitez's side will be determined to bounce back after their disheartening Champions League exit
The Partenopei suffered an unfortunate exit from the Champions League in midweek, with their 2-0 win over Arsenal ultimately not enough to see them into the next round due to Borussia Dortmund's late victory over Olympique de Marseille.
Rolando - who spent time with Napoli last season prior to his loan move to Inter from Porto this summer - believes Rafa Benitez's side will not be unduly affected by Wednesday's disappointment and will be eager to record a positive result in Walter Mazzarri's return to Naples.
"I don't think they'll be demoralised," the Portuguese told Inter Channel. "They know they did extremely well in their group. It's the first time a team has finished with 12 points and not qualified, but they're aware of how good they are and they'll want to prove that against us. It won't make any difference to us though because we're determined to play our own game.
"It will be really hard because Napoli are having a great season. It's always tough at the San Paolo, but we're going there to try and play our game and we'll see what happens.
"The crowd is amazing and makes it difficult for the opponents. I saw what it was like last year and that's why I say it won't be easy, but we're confident about our chances."
Inter sit four points behind third-placed Napoli in the Serie A table prior to Sunday evening's clash, which kicks off at 20:45 CET.