Early departure from Venice

We stayed at the Hotel Flora in Sept. It was close to St. Mark's Sqaure, but down a very quiet alley and had a lovely garden to have breakfast in. Our last night we spent enjoying the music in St. Mark's Square. Our hotel ordered us a water taxi and the bellboy took us to it. It was suppose to cost 100 euro, but the driver said that since it was before 8am he charged us and extra 20 euro. We took the taxi at around 7 am. It was fun to see the city zipping through first the Grand Canal for a bit and then all these back waterways until we were finally on the north side of the island past the burial island and then following the bouy markers to the airport dock. We saw the city coming to life and the sunrising. Looking back this took the place of the gondola ride we did not do although my husband rode a traghetto for 1/2 a euro when he was exploring the city. Email the hotel where you are planning to stay to see if they could order you a water taxi at 4:40am and what they would charge.

(continue) When you get to the airport dock men will approach you and ask if you want to take their van to the airport for and addition 20 Euro and they will escort you and your luggage right up to you airline check in. We did it because we were tired. If you look up and to the right a little ways you can see the walkway to the airport. If you are up to the walk and dragging you suitcase, it is suppose to be a 10 minute walk. If I had to do it over again, I would still do the water taxi ride and I will always have the happy memory of my last night listening to the music at Cafe Quadri in St. Mark's Square.

Cathy,
The problem is that you will pretty much have to rely on a water taxi, which is going to cost a lot. That was something my wife and I had to consider for our trip, since the only way to make the Air France flight leaving Paris was to leave early in the morning.
Instead we decided to fly out from Verona, which was a 20 EUR tax ride from our hotel, the hotel was cheaper than Venice for that night, and the train ride to Verona was WAY cheaper than the early morning water taxi. Unfortunately this won't really help you at this point, but will hopefully alert others who look to fly out of Venice, but can only take early flights.
As far as where you stay in Venice, it doesn't really matter as you'll have to hire the water taxi from wherever that is - and time and cost probably won't be any difference where you are on the island.

You could also stay in Mestre the second night, which is the closest town on the mainland. And then a cab to the airport. It will be cheaper, but you will eventually have to leave Venice for the night, which will limit your time there even more.

I just read Kent's response but Kent it was worth it to both my husband and I to have our the last night of our Italy trip spent in the city of Venice. We had paid all the rest of the money for the trip. We didn't take a Gondola ride, we did this instead. The water taxi ride and seeing the back canals and the north bay area was worth it to us. We do a lot a boating at home, so I got a added pleasure watching the water taxi driver navigating his way around. I guess it is a choice each individual has to make. When we were in Munich at the end of a trip a few years ago we did opt to stay by the airport for an early morning flight. I had been to Venice without my husband years ago while on a very tight budget. I was glad we decided to splurge on for our last night and morning. Venice is one of my favorite cities and I don't think I'll get back there again.

That's exactly why we picked a flight home from Venice with a 23 hour layover in Copenhagen (with SAS). It leaves Venice at a very civilized 3 pm. And we'll wander around the Tivoli Gardens in Copenhagen near our overnight hotel. (At least that's the plan.)

You could stay at hotels at the airport. They have transportation into the airport. Of course, to visit the main island, you would have transit to and from the airport area. ACTV has a bus from the airport to Piazza Roma for about 3 Euro.

If you stay on the main island, Alilaguna has ferries to the airport that leave at 3:40am from San Marco on the Guidecca Canal. It arrives at the airport at 5:00am. About 12euro each + 6euro for luggage.

As mentioned above, Line 5 of the ACTV land bus system leaves Piazza Roma at 4:40am and arrives at the airport at 5:05am.

Both are a bit tight but you have 90 minutes to get checked in.