There are direct express trains from Milan and Rome to Palermo, Catania, and Siracusa. The Rome-Palermo and Rome-Siracusa trips take at least 10 hours. After Naples, the run is mostly along the coast, so try to book a window seat on the right if you're not on an overnight train. At Villa San Giovanni, in Calabria, the train is separated and loaded onto a ferryboat to cross the strait to Messina.
Within Sicily, main lines connect Messina, Taormina, Siracusa, and Palermo. Secondary lines are generally very slow and unreliable. The Messina-Palermo run, along the northern coast, is especially scenic. For schedules, check the Web site of the Italian state railway, FS (892021. www.trenitalia.com).