Rome to Volterra

The fastest way to get there would probably be a rental car from FCO to Volterra. By public transportation, one way would be to return to Rome Termini on the Leonardo Express and buy a ticket from Rome to Volterra. CLICK HERE to see the train schedule.

One important note. I don't believe that there is a train station in Volterra even though Trenitalia shows one. I believe that it may be in nearby Saline. If correct, you can take a bus or taxi from Saline to Volterra.

If you're planning to drive (as suggested by dropping off friends at the airport), check www.viamichelin.com for suggested routes. Their recommended route along the coast takes just under 4 hours while their quickest route via A-1 autostrada is 13 minutes faster. One of those sounds like your quickest way to get to Volterra. Public transportation will take longer, as it involves a combination of train and bus or taxi. There's the route Larry has suggested, or you could take the train to Florence and bus from there. Florence train and bus stations are only a short walk apart. Note that buses are sparse on Sundays.

Frank's idea is better than my public transportation idea. Rome to Florence on the Eurostar takes 1hr-40min. Then, you walk about 1000' to the SITA terminal and take the SITA bus. CLICK HERE to see the SITA bus schedule from Florence to Volterra.