Argentina striker Higuain, 25, is set to move to the Stadio San Paolo for a reported 40million euro (?34.5million) on a five-year contract after scoring 107 league goals in six seasons with Real Madrid, while Liverpool goalkeeper Reina prepares to be reunited with former Reds manager Rafael Benitez on a season-long loan deal.
A report published on Gazzetta.it shows Higuain wearing a Napoli scarf while being mobbed at Rome's Fiumicino airport and it is understood he travelled to the city's Villa Stuart sport clinic to undergo a medical alongside 30-year-old Reina on Wednesday afternoon.
Reina's agent, Manuel Garcia Quilon, told Gazzetta.it: "He's happy to reunite with Benitez because he's known him for over five years from their time in Spain and England, and they worked very well together."
Higuain, who declared his intention to leave the Santiago Bernabeu towards the end of the 2012-13 season, had also been linked with Premier League club Arsenal while Reina's chances of first-team football at Anfield appeared increasingly limited following the arrival of Simon Mignolet from Sunderland.
Napoli have already signed winger Dries Mertens from PSV Eindhoven and both forward Jose Callejon and defender Raul Albiol from the Spanish capital club as the Serie A runners-up rebuild for a title challenge by reinvesting the reported 64million euros (?55million) earned from striker Edinson Cavani's transfer to Paris St Germain.