"I'm not going to have them in the African Cup of Nations or the South American championships," Napoli president de Laurentiis said in an interview broadcast on Tuesday night.
"Don't talk to me about Africans anymore," de Laurentiis told business website Wall Street Italia.
"I wish them well, but either they sign a waiver for the African Cup or else..."
"Between that tournament and the World Cup qualifiers in South America, these players are never available," adding We are the idiots who pay the salaries to send them to play for others."
Several key Napoli players are African internationals.
Last season they lost Senegalese defender Kalidou Koulibaly, who has since left for Chelsea, and Cameroonian midfielder Frank Zambo-Anguissa to the African Cup of Nations in January and February.
Nigerian striker Victor Osimhen missed the competition after testing positive for COVID.
The African Cup of Nations is held every two years in January and February with the next postponed edition taking place in January 2024 in the Ivory Coast, during the European season.
The Copa America is also played every two years with its finals in June and July but World Cup qualifying is held during the European season.
While the 10-team Copa does not have a qualifying tournament, the African Cup of Nations does, increasing the number of games for players.
Clubs are obliged to allow their internationals to join their national teams during official international breaks.