The Uruguayan forward finally ended months of speculation surrounding his future by joining the Ligue 1 champions on Tuesday for a reported €62m (£54m).
At his unveiling in the French capital, Cavani reserved a line for his former club by saying that he will always have affection for the Naples outfit.
"I want to tell the people of Naples that I will always carry them in my heart," Cavani told reporters.
"I love Naples and I want to come back one day. I love the people and I always will do, but today I am a PSG player and I will give everything for these colours.
"I wish Napoli all the best and I hope they can win more trophies."
The 26-year-old finished as top scorer in Serie A last season, netting 29 goals as the club finished second to Juventus.