Rome to Venice Air or Train ? and Booking advice

Definitely take the train. There are many and you don't have to get from the Marco Polo airport to Venice. Other folks can give you hints about advance purchase for train tickets; I don't worry about it and just buy at the station once I'm ready to go.

I believe that a ticket for EuroStarItalia comes with a "mandatory reservation".

The Leonardo Express leaves Fiumicino at 6 and 36 minutes past the hour. The trip to Roma Termini takes 31 minutes. If you're lucky enough to breeze through passport control and luggage claim, you POSSIBLY could catch the 10:36 train (but I wouldn't count on it). If you make it, you could leave Termini at 11:30, change at Bologna Centrale, and arrive at Venezia Santa Lucia at 16:47. A safer bet would be to plan on taking the direct train that leaves Termini at 12:50 and arrives at 17:17.

The simplest thing to do would be to buy all your tickets at the station at the airport. It's possible to get Amica fares (20% discount) for Roma-Venezia by booking ahead at www.trenitalia.com/en/index.html; but registration is required on the site, a process that often is problematic. You can book up to 60 days in advance.

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There are no budget airlines that fly to Venezia from Fiumicino. However, Alitalia offers a one-way fare of $132 US. Depart at 12:30 and arrive at 13:45. Of course, you still would have the time and expense of getting from the airport to Venezia.

If I were doing this, I'd take the train. I'd use any free time I had at Termini to buy food and wine for a picnic on the rails and enjoy a comfortable and relaxing ride that would take me right to the heart of Venezia.

Many thanks to all for your kind help.
Looks like I've got lots of options either way. Although the timing is tight, I might be able to catch the 10:50 am train. Failing that, there are plenty of planes from 12:30 pm on that fit the plan. I guess Volare doesn't fly Rome to Venice any more?
Cheers!

Eryk - Air One (a discount Italian airline that I find to be MUCH nicer and more reliable than Alitalia) flies from Rome to Venice. You have to go to another terminal in Rome, but it's only a short walk. Right now Air One is offering a EUR 72.56 one way fare (EUR 20 + taxes) on their May 22 1:15pm flight arriving at 2:15. Getting to central Venice is easy, either by EUR 3 bus to near train station or EUR 6 - EUR 12 (depending on destination) boat. I'd seriously consider Air One, as it gets you to Venice sooner than the train. If you're returning to Rome airport 3 days later, the return airfare is the same. Note that if you book on-line with Air One, you'll need a credit card with first and last name only (no middle name or initial) and you'll have to print your e-ticket from their website.

IMO, Tim has the best thought. Get on to the Eurostar as fast as you can and get to Venice. You can sleep a little on the train or sleep when you get to Venice althought that may be difficult once you walk out of the Venezia Santa Lucia train station. And, if you can stay awake a bit longer you can easily learn your way around during the afternoon. The Eurostar and other high-speed trains all require date, time and seat reservations but you can do all of this at the same time. You can accomplish this in English at the ticket machine with your credit card or go to the ticket window and say "Venezia Santa Lucia and Eurostar". Agree on the time and you will be sold your ticket(s). If you change trains anywhere during the journey you will have a ticket for each train. For example, Rome to Bologna to Venice will get you two tickets. It's not difficult.

This is a pretty common topic. You can see it at this thread:
http://www.ricksteves.com/graffiti/helpline/index.cfm?topic=7551
It has a link to another thread too.
Having taken the Eurostar from Rome to Venice, that will remain my choice. For the most part, the time will be a wash with time to get to the airport from town, getting there early enough for the flight check-in, flying, and then getting into Venice. The Eurostar drops your right on the island of Venice.

My saying that no budget airlines fly Fiumicino-Venice turned out to be wrong. Thanks for correcting me, Frank. I only used whichbudget.com to search for flights. I should also have checked skyscanner.net. Air One is listed there.