Suggestion Required for a 11 trip to Italy and few queries

If memory serves correctly, Florence, San Gimignano, and Siena are all fairly close together. Although we haven't done San Gimignan and Siena as day trips from Florence, it might be worth thinking about that. Or basing in Siena and doing day trips from there. The reason for that suggestion is that relocating from one town and hotel to another usually takes a good bit more time than anticipated. And that is time that is just lost. Don't mean to be a downer, just food for thought.

You might visit San Gimignano as a daytrip from either Florence (1.5-2 hours by bus, 1 change) or Siena (1.25 hours by bus, direct) to minimize time spent changing hotels.

Just a thought: the train ride from the CT area (La Spezia) to Venice is 5-6 hours, but CT to Florence is 2.5 hours. You could consider starting your trip in Venice, then moving to Florence (2-3 hour ride to Venice), which is well connected to all your other locations by train or bus rides that are only a few hours. If you're interested in that option, you could look at the details for traveling between your other locations to determine the order, and fly out of Florence.

Drop the overnight in San Gim ; add it to Venice. Given your timeframe I think you need to Skip San Gim entirely unless you skip Siena instead.
Feel like even doing so you need a couple more nights, good chance you will get some rainy periods.

If photography is important you will need more time most everywhere to have a chance at good light in each place.
Given the hassle of getting to CT and then getting from there all the way to Venice, I would want 3 nights in the CT and think you should give that serious consideration.

I imagine any Val D'Orcia photography tours worth taking meet before sunrise ; and the meeting place will be an hour+ south of Siena making that tough for you to get to from Siena and you would need a car.
The area between Pienza and San Quirico is really all you need ; most every shot you have seen is from this very small area.
Pay for my flight and I would be happy to guide you around :)

I remember being all alone on a field at the Belvedere overlook/property as a van screeched up about 10 minutes past sunrise which I thought at the time was too late and about 15 people with tripods and a tour operator jumped out and descended on where I was standing.
A few rudely even ahead of where I was standing in my cameras field of view.
It turned a beautiful moment for me into a chaotic one.

We all caught some nice mist in the valley as the sun rose on the horizon and the fog lifted ; one of the very rare places where 30 minutes past Sunrise was better than Sunrise itself though the fog lifting was gone in about 15 minutes after it started.

If you are fine with day time photography in the Val D' Orcia there is no reason to pay for a guide other than transportation if you have no car.

Thanks a lot.

Yes, I am planning to visit San Gimignano from Siena - by staying an extra day there.

I am exactly looking for an guide/operator who will take me to Val d'orcia before Sunrise. I want to start from Siena around 5 in the morning. Sunrise is at 7.30 am and it is 40 km from Siena. I could stay at San Quircio d'Orcia but then again I want to avoid relocation.

I have planned to return to Florence from Cinque Terre on the morning of 30.09.2017 - and witness the Carro Matto. And then proceed to Venice.

Another thing, that is on mind is to visit Volterra from Siena instead of San Gimignano. An acquaintance of mine who visited the place last year told me - "the place looks great from outside and from the top - but the street scene have become very touristy with shops, food joints and crowds - and you wont feel the medieval atmosphere anymore"

I would do:
FLORENCE 3 nights.
Would rather skip San Gimignano and not Siena
SIENA 2 nights (day trip to Val d'Orcia.
Would not go to Cinque Terre but rather to Porto Ercole or Porto Santo Stefano or to Isle of Elba. (2 nights) (you might want to rent a car, train is also possible to Orbetello a d then bus to Porto Santo Stefano or Porto Ercole. For Isle Of Elba you have to go to Piombino , take the boat (1 hour). Rent a car or a motobike to tour the island although bus are good on Elba.
Venice for your last days

I would do:
FLORENCE 3 nights.
Would rather skip San Gimignano and not Siena
SIENA 2 nights (day trip to Val d'Orcia.
Would not go to Cinque Terre but rather to Porto Ercole or Porto Santo Stefano or to Isle of Elba. (2 nights) (you might want to rent a car, train is also possible to Orbetello a d then bus to Porto Santo Stefano or Porto Ercole. For Isle Of Elba you have to go to Piombino , take the boat (1 hour). Rent a car or a motobike to tour the island although bus are good on Elba.
Venice for your last days

Fly into Florence. Stay for 3 nights.
Go to Siena. Stay 3 nights. (day trips to San Gimignano and Val d'Orcia)
Go to Cinque Terre. Spend 2 nights.
Go to Venice. Spend 3 nights. Fly out Venice.

Note that Florence is only for internal European flights. Rome/Milan/Venice are gateways for flights from Asia/Americas.

Check out opinions on the downside of early morning flights out of Venice.