From Sorrento to Montepulciano... pick up rental car in Naples or Florence?

There is a ZTL also in Naples (and in Montepulciano and in any other town in Italy), but driving out of Florence will be ten times easier. To give you an idea: Italians can easily spot the ZTL signs, but some plainly refuse to drive in Naples.

I'd check if you could pick the car in some town north of Rome, try to find one that can be reached by train.

our plan is to drive the rental to Venice and drop it there.

That makes sense only if you are going to stop somewhere along the way, or if you are interested in viaducts and tunnels. Lots of.
Otherwise I'd try to drop the car off in Florence and take an high speed train to Venice.

If you prefer to drive, be aware of the Tutor System on the A1 motorway. There are also 3 speed traps on the causeway between Mestre and Piazzale Roma, the parking lot on the main island where most rental agencies are located.

Pick car up at Naples airport and the autostrada is very close, easy.

From Naples central station it's 3 hours by train to Florence, then at least a 2 hour drive to Montepulciano.
From Sorrento to Naples central station, you'd take the local circumvesuviana train which takes over an hour (up to 1.5 hours) to Naples central station and runs about every half hour. Since it's often late, you have to allow lead time to transfer to Trenitalia in addition to the 10-15 minutes to transit the station itself.

It's about 4 hours by car (per google maps) from the Naples airport to Montepulciano. I'm not sure what the options are to get there from Sorrento, maybe a direct bus or shuttle service? That would seem to be the better option

We drove from Civitavecchia to Sinalunga (Tuscany), but that's because we got off a boat. We stopped for short visits to Viterbo and Orvieto along the way. (Boats dock early, for turnarounds!) Some people might recommend getting the car in Orvieto, but I agree that touring with luggage is not the same as making daytrips from your hotel or villa. The point is that Orvieto has a massive multi-deck garage with escalators to the town.

There was once a post here saying that the Florence ZTLs were not a big problem, but I have no experience with that. No sane person would drive a rental car in downtown Naples-it's a third-world city with regard to DRIVING. I can't imagine any reason to make the entire drive (which will take longer than the Google Maps estimate) from Naples to Florence. What is the point? American freedom of expression on the mighty open road? Visits along the way? Passenger with a bad knee? Large number in party with corresponding fear of train prices?

I did drive from Sinalunga to the Rome airport for the trip home, and the autostrada was OK, but not especially scenic or useful, and the lanes are not as wide as they are in the US. The truck traffic is more speed restrictive and "threatening" (only because of dimensions, not personality) to the cars.

At least May 7 is a Saturday, but driving around Rome is no pleasure any day of the week. You can save a LOT of time with the Frecciarossa trains, at the price of an advance discounted ticket that is not changeable or refundable. Time is money on vacation.

Any reason you wouldn't pick up rental car in Sorrento? AutoEurope shows available there.

In the past there was no one way drop fee within Italy, but that may not be the case now. Could be as much as an extra $200 to do a one way rental.

You may want to check out the various scenarios to see how that may affect the rate for your dates and city combinations.

To avoid driving in or out of large cities, we took the train from Florence to Chiusi and picked up a rental at Hertz a couple blocks from train station. Easy drive from there to Montepulciano where we stayed 3 nights and drove the car on day trips around Tuscany. We then returned the car to Chiusi and took the train to our next destination which was Milan. Never had to drive in big cities or worry about ZTL areas.

I rented a car in Naples a few years back. It was easy to do, and the distance from the AutoEurope rental place to the Autostrada was very short. With that said, factor in 1.5 to 2 hours getting the vehicle, and then sitting on an Autostrada for several hours watching trucks pass you. If the thought of traveling from Bakersfield to Stockton, CA or from Newark, NJ to Baltimore, MD sounds like fun, then be my guest.

Trains are much easier, and nothing says Italy better than eating a mortadella panino and drinking a Peroni beer as you watch the miles (kilometers) fly by.

Then, when you actually NEED a car, rent one in Orvieto or some other place in Umbria or Tuscany.

Thanks for all the responses! I think it's clear, driving from Naples/Sorrento area up to Montepulciano is NOT ideal! The goal here is really just to have a car for the Tuscany portion of our trip. So based on all the feedback, I think we'll take the train from Sorrento to Chiusi and pick up the rental car there for the quick drive into Montepulciano. After our time there, we'll return the car to Chiusi and take the train up to Venice. Any red flags with this plan?

Well, I get the idea you've already read up on general car rental annoyances in Italy. I wonder if a rental agency in a smaller city will have little choice of vehicle? I mean, it's quite common for the car you thought you reserved to be unavailable upon your appearance at the counter, even in the US. Luckily, getting a too-big car is not a huge penalty in Tuscany. But can you drive a standard transmission if that's all they have? I've been refused the car I reserved at the Frankfurt airport! They wanted me to take a giant (automatic) van instead of a sedan. I had to wait for another (standard) sedan to be checked in and cleaned.

Have you been to the Trenitalia site to get an idea of the train routings and prices? I've never been on a train at Chiusi. It is very convenient to get bar-coded print at home tickets, but you have to be aware of change rules, if changes are even permitted.

Edit: I'm only adding this so I don't sound like a crank! My wife went to (near) Brussels several times a year for a multinational Fortune 100 company with an EXCLUSIVE WORLWIDE, one-company major car rental agreement. NOT ONCE in five years did she ever get the automatic transmission she reserved for her group. She'd driven a standard for years. But she had to do all the driving for her junior staff because they were helpless with the Standard.

Unlike Tim, I had a good experience with car rental in Chiusi as did a friend who rented a few months earlier. Train trip to and from Chiusi was also easy. A car is needed to enjoy Tuscany and driving there was fun and scenic. Enjoy your stay.

Any red flags with this plan?

1. Backtracking. You'd drive away from Florence to take a train back to Florence, where you'd transfer to the direct high speed train to Venice.
2. There is only one direct train from Chiusi to Venice, and it's a night train that arrives at S. Lucia station at 6:25 AM

Pick the car in Chiusi, drop it off in Florence, either downtown or at the airport.

Thanks again all. I've driven in Europe before, just not Italy and have no issue with manual transmission. Looks like Sorrento - Naples - Chiusi via train... pick up rental car in Chiusi. Then return car and go Chiusi - Florence - Venice via train.

Thanks again!