"KING KEV IS HERE," Napoli declared in a series of posts on X on Thursday.
The 33-year-old De Bruyne's contract at Manchester City has expired but Napoli did not announce the length of his new contract.
Around 150 fans welcomed De Bruyne on his arrival at a clinic in Rome for his medical. They chanted his name before also singing about Napoli being champions after the player had gone into the facility.
At the Italian giants, De Bruyne will reunite with Belgium teammate Romelu Lukaku and follow in the footsteps of former Napoli great Dries Mertens, an ex-Belgium international.
In Napoli's midfield, De Bruyne can team up with Serie A player of the year Scott McTominay, who made a highly successful move from City's neighbours and rivals, Manchester United.
Known as one of soccer's most complete midfielders, De Bruyne was named the best player in the Premier League for the 2019-2020 and 2021-22 seasons and is generally considered one of the finest players of the EPL era.
In 10 seasons at City, he helped City to six Premier League titles, two FA Cups and a Champions League trophy.
The addition of De Bruyne may have been one of the reasons that convinced Napoli coach Antonio Conte to stay on for another season after he had considered rejoining Juventus.