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Siena to Positano

Part of our trip in Oct will involve going from Siena to Positano(3 days there) in a day. Should I buy a ticket from Siena to Naples and then the circumvesuviana or ticket to Rome? Stop at Pompeii on the way or go on another day? Any opinions on best way to do this?

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I think to do your travel and Pompeii in one day would be a stretch. It is about 5-6 hours from Siena to Naples, another half hour or a little more to get to Pompeii. Figure Pompeii is at least 2 to 3 hours, then Positano another hour or so, a very long day. You will also have to stow your bags someplace. My preference would be to get directly to Positano, then pick one day to get up, head to Pompeii, take a leisurely tour, then on to Naples, see the Arch. Museum where the artifacts are, have a nice lunch (classic pizza) then back to Positano for a little time on the beach and a great meal.