The 28-year-old has established himself as a key member of the Partenopei's squad since joining the club in 2007, notching up 165 Serie appearances over the last five seasons, and appearing 43 times in all competitions during their most recent campaign.
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The Uruguayan was named among the substitutes for his side's 3-1 friendly win over Braga, but breached protocol by returning to the dug-out late after the break, and Mazzarri was adamant that all players must follow his directives.
"The rules must be respected by all, the boys know they have to be present. I was calling for him, but no-one knew where he was," Mazzarri told reporters after the game.
Several players have moved between Inter and Napoli in recent years, including Macedonia international Goran Pandev, who made the switch from Inter to Napoli earlier this summer.