15 Day November Trip 2 adults

It will work. But have you considered booking a multicity ticket into Rome and out of Venice ( or vice versa) to avoid the time lost in backtracking?

Fly in to Venice, out of Rome
Easier to arrive at VCE than depart

Montepulciano area much better with a car unless you plan to stay put in town

hey hey dmhughes50
have you bought your airfare already? you should do a multi-city flight (into one city and out of another, not 2 one ways). no backtracking. start in venice and end in rome or start in rome and end in venice.
look at fly in and fly out times, check in is 3-4pm and check out is 10-11am. usually early morning flights out of venice with considering transportation issues to airport. keep all rome days together at end if possible
backtracking venice to rome on train is 3-4 hour ride, it's your decision with lots to think about. good luck & enjoy
aloha

Backtracking to Rome for 2 reasons:
1) We are train nerds (my partner prefers aficionados) so taking the train back is more a part of the trip rather than just transportation.
2) We are picky about non-stop flights and FCO - ORD is our best option

I chose Montepulciano over Siena. I like the smaller town experience. I have also found an ebike company that we can use to explore outside the city. http://www.urbanbikery.it/en/
Would you suggest another hill town? Or talk me into Siena?

If you're train nerds then maybe treat yourself to First Class- it's a lot quieter and you have more room.

For Rome, we stayed in Trastevere our first time, but ever since then have stayed in the Testaccio neighborhood on every trip. It’s less touristy, but still convenient to sights. For your last night, are you planning on staying in the center, then taking an early taxi to the airport, or staying right at the airport, like at the Hilton? We’ve done both. It kind-of depends on just how early is your flight out, and how much you’re willing to spend on lodging and transportation.

In Venice, we’ve stayed in the Ghetto neighborhood, and the Arsenale neighborhood. Ghetto was slightly more convenient for strolling and for reaching the center or train station; Arsenale was strictly locals (plus us two tourists), and felt very non-touristy.

Something that I remember about that train route is the surprisingly large amount of time spent in the dark between Florence and Rome because it’s mountainous and there are many, many tunnels.

It's absolutely fine and November is a good time.

What are thoughts on staying in Monti while in Rome?

I chose Montepulciano over Siena. I like the smaller town experience.
I have also found an ebike company that we can use to explore. Or talk me into Siena?

I own and e-bike but you could easily end up walking back into Montepulciano from down below, it's a steep climb! I think the choice depends very much on what you want to see while you're there, I personally would choose Siena because it has so much art & history to offer and it is very easy to access from Florence without the hassle of renting a car, whereas M is basically a small hill town with excellent wine. Both places get a lot of day trippers, but the evenings and mornings will be lovely.

Monti - Sure, why not? It's a very popular destination so won't be very quiet. I would not stay in Trastevere, it's jammed in the evenings. I prefer the location of Hotel Smeraldo. Personally I love staying in the historic center.

If you use the tool bar on RS home page to look up Monti hotel, there are some reviews. Here's one. https://community.ricksteves.com/travel-forum/italy/hotel-in-monti-area-final-puzzle-piece

I would reconsider your choice of Montepulciano in November. Sunset in Florence in November is 5.05 pm at the beginning and 4.39 pm at the end of the month. That means short days and long evenings. I would NOT recommend biking on rural roads when light is fading. And you may not find enough variety for 3 long evenings in a small hilltop town. Siena has a variety of sights, day trips by bus to other hilltop towns, and lots of restaurant choices for dinners and areas to wander in the evenings.

Thanks for the insight on Montepulciano. Based on your comments, I think I will go back to my original plan of Siena! Would love some suggestions for lodging in Siena.