Ancelotti travelled to Rome on Tuesday evening to meet with Napoli chairman Aurelio De Laurentiis regarding the upcoming vacancy at the Serie A outfit.
Despite holding positive discussions with current manager Maurizio Sarri last week, De Laurentiis is now consigned to losing the 59-year-old this summer having failed to agree a new deal
Sarri is set to depart having led the Partenopei to a second-place finish in Serie A, with their final points tally of 91 the most for a team not to have won the Scudetto.
He currently has an offer from Zenit St Petersburg to replace new Italy national team boss Roberto Mancini but is holding out for Chelsea, where he remains the Blues' primary choice to replace Antonio Conte.
Conte is still expected to depart Stamford Bridge this summer despite winning the FA Cup, and Sarri remains the frontrunner among the Chelsea hierarchy.
Ancelotti is now closing in on signing a two-year deal with Napoli, marking his return to Italian football for the first time since leaving AC Milan in 2009.
He will take over a Napoli squad that looks set to be torn apart this summer, with Pepe Reina close to joining Milan, Marek Hamsik hinting he could move to China and Jorginho on Pep Guardiola's radar at Manchester City.
Faouzi Ghoulam, Elseid Hysaj and Kalidou Koulibaly have also been linked with Premier League moves while the likes of Dries Mertens, Allan and Lorenzo Insigne are unlikely to be short of suitors.