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Naples to Siena train or bus combination?

While researching this part of our trip, I discovered many different ways to travel to Siena from Naples. Some of the connections where only 5 minutes apart. I like the idea of a train then a bus that travels through the countryside. Any suggestions that will get us there by late afternoon.We do have to get from Positano to Naples 1st. Gracie

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There are two ways to get from Positano to Naples. First, is the SITA bus from Positano to the Sorrento train station. Runs frequently daily and less on Sunday. From Sorrento to the Naples train station, you take the Circumvesuviana train. It's local into the train station. Once in the Naples train station go upstairs for the Trentialia trains. The second choice is to take the ferry from Positano to Naples. It's about a mile walk from the ferry dock to the train station.

At the Naples train station, you have two more choices. First is a train all the way to Siena. Second is a train to Rome, a metro to the Rome Tiburtina train station where you go outside to the bus stations and take a bus from Rome to Siena. For Rome Termini to Siena, CLICK HERE to see a train schedule. Note that on some runs, you do transfer to a bus in Chiusi for the ride into Siena. Standard 2nd class fare is 64.10Euro for this journey.

For the SENA bus, you take the train from Naples to Rome Termini (36.10Euro). Then go downstairs and take the Metro line B 4 stops to Tiburtina. Go outside to the stations for the multiple bus lines and look for the SENA bus. Looks like six runs a day. Looks like 18.50Euro for the ride.

By the way, travel time is about the same either way. Second, the bus station at Siena is much closer to the city than the train station.