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Tuscany Itinerary for 2025: Would love your input and thoughts.

I'm in the preliminary planning stage for a trip to Tuscany, no dates set yet but it will be sometime in late Sept. or early Oct. 2025. It's a birthday surprise for my husband so I can't ask him for his input. We've been to Tuscany before and enjoyed it a lot but would like to spend more time there.

Day 1: Depart US for Florence
Day 2: Arrive Florence pick up car at airport: night in Volterra or someplace nearby (advantage staying in town can walk to dinner, don't have to worry about drinking and driving) disadvantage parking is an issue) or stay at Agriturismo near Volterra (4nights)
Day 3: Take it easy and explore Volterra (been here before)
Day 4: Day trip to Pisa and Lucca (skip Pisa and go tomorrow) entire day in Lucca?
Day 5: Day trip to San Gimignano (been here before) and Pisa

Day 6: Switch locations to other part of Tuscany: Maybe something outside of Siena or Pienza or in or near Montepulciano (Agriturismo or Country side B&B) (5 nights)
Day 7: Heart of Tuscany Drive
Day 8: Brunello Wine Country Drive
Day 9: Crete Senesi drive
Day 10: Siena
Day 11: Drop car Florence airport night in Florence stay B&B in Florence (been here before) (1 nights)
Day 12; Fly home
I can add a few more days if necessary
Thanks you in advance for your thoughts and input.

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Sounds like a wonderful plan. Are you sure you want to drive right after your flight? I would be concerned about the safety of driving while tired from jetlag...but I don't manage to sleep during flights.
On day 4 you might still be tired from jetlag so it would be a good idea to plan for a short drive to just one destination.
While in Pisa, give yourself time to do Rick's walking tour as well as visiting the leaning tower, baptistery, and church. The walking tour leads you to visit parts of the town and is worthwhile, IMHO. Be sure to book an entry time on advance to climb the leaning tower.
Maybe you could add an extra day to explore new sites in Florence before departure. You have been there before, but there's so much to see.