Amalfi Coast Itinerary

Yes, but why waste your time traveling?
Ferry to Napoli, taxi to Napoli Centrale, train to Roma is 2nd best way. Best, if you have the money, is helicopter.

Why Positano?

Ferries from Positano can be and are cancelled due to sea conditions so it’s not the best place to transfer to Rome from
Ferries don’t run after a certain time of day either and stop running at some point in October

Travel from Pompeii to Positano will require local train to Sorrento then bus or ferry to Positano -that will take a couple of hours
Positano is worth a few hours at most IMO

Another option is ferry or bus from Positano to Salerno then direct fast train to Rome-

Or hire a driver to Salerno

I hope you are not flying out of Rome on the day you leave Positano-it’s just not possible

Thank you. Where would you stay on the Amalfi coast if not Positano? (Not flying same day as Positano to Rome - next day)

Could you clarifyi your plans?
Are you staying in Positano (or elsewhere on AC)?
How many nights?

Amalfi ( town ) would be my choice

Unless you want to see Capri.

If ferries are still running, I would go through Salerno both ways. You can take the circumvesuviana from Naples to Pompeii, store your luggage, and then go to the other end of the ruins (taxi might be easiest with luggage) to take the normal train to Salerno, then a ferry to Positano (and back the same way to take the train to Rome). If ferries aren't running at that time of the month, it's just annoying to get to Positano at that time. I would probably choose to stay in Amalfi (for ease of bus transportation, as it's the terminus of the lines on the coast) if they aren't running. But for the EASIEST way, I would pay for a car to take you to Pompeii, wait, and then take you to your AC destination.