Cavani, who finished top scorer in Serie A last season with 29 goals, landed in Paris on Monday morning and was put up in a luxury hotel previously used by David Beckham during his short spell with PSG last season.
It is expected that the Uruguay international will complete his medical and sign a five-year contract later on Monday.
If PSG do complete the formalities of the deal then the signing of Cavani will be the most expensive transfer in the history of French football.
The previous mark was set earlier this summer when newly-promoted Monaco paid Atletico Madrid 60m euros (£52m) to sign Falcao.
Cavani has spent three prolific seasons with Napoli having joined the club from Palermo in 2010, scoring 104 goals in 138 games for the southern Italian side.
"He (Ibrahimovic) won't play with Cavani," said De Laurentiis. "He's already been promised to other horizons."