The Colombia star's future is up in the air as his two-year loan spell at Bayern Munich looks set to end without the German club making the move permanent, while he does not appear to be counted on by those at the Santiago Bernabeu.
Liverpool, Manchester United and Juventus have all been linked with a swoop for James, but it seems Napoli will be the first to launch a bid after Ancelotti brought up the possibility of bringing the 27 year-old to Serie A.
"We have always said that we need two full-backs and one striker," De Laurentiis said. "James Rodriguez fits the image of what Carlo Ancelotti wants.
"I don't know how much he 100 per cent answers our needs, but we certainly can't put his skill in doubt. At a certain point one must then empower his coach.
"If he [Ancelotti] wants him for Napoli, it is because he knows how useful he [James] can be, even if he is very expensive. I said, 'let's go ahead'."
James, who is on international duty at the Copa America, said that he is unsure where his future lies, but De Laurentiis confirmed he will be in touch with the player's agent, Jorge Mendes, to open discussions.
PSV winger Hirving Lozano is being considered as an alternative if a move for James falls through, though De Laurentiis made it clear the club cannot afford to buy both players.
"If I don't reach an agreement with Jorge Mendes, I'll talk to Mino Raiola about Hirving Lozano," De Laurentiis said. "We can't take them both.
"We already have a series of players we can't ignore. We have to sell first and then we can buy.
"Mendes is perhaps the best agent in the world today. He is also a friend. I think James will be very expensive, but if we have to make a sacrifice, we do it. For one player, you can do it."