The Senegal international has long been linked with a move to the Premier League, with speculation having resurfaced during the current transfer window.
Jose Mourinho is considered to be in the market for defensive reinforcements at Old Trafford, while former Napoli boss Maurizio Sarri is now in charge at Stamford Bridge.
He has already completed one raid for Jorginho and may be tempted to bring another familiar face with him to west London.
De Laurentiis, though, has no intention of selling, with one big-money approach having been rebuffed.
He told Radio Kiss Kiss: “It’s true, we had a €100m bid from the Premier League for Koulibaly, but we’re not negotiating his sale.
“He’s a very good person and we’ve never had problems with him.”
While moving to rule out one sale to the Premier League, De Laurentiis has also distanced himself from a possible move to bring in a new striker from the English top-flight.
It has been suggested that three options currently on the books at Chelsea are among those under consideration in Naples.
De Laurentiis has, however, quashed talk of moves being made for Michy Batshuayi, Alvaro Morata or World Cup winner Olivier Giroud.
He said: “Are we interested in Batsuhuayi, Morata and Giroud? Quite false!”