Italo Treno provides a direct railway service from Naples to Florence. Just take one of Italo Treno bullet trains that depart hourly starting at 05:20 am. They cover the distance between the two cities in about 3 hours, which is the most comfortable and fastest way to get to Florence.
Which station in Naples goes to Florence?
Trains to Florence depart from Napoli Centrale. You can get there either by metro (Line 1) or ANM buses and airport shuttles. From the station, the trains depart every hour, which lets you adjust your plans conveniently.