As a first time traveler to Europe I'm a little confused with transportation out of Venice. Our hotel is off Piazza San Marco, 2 people are traveling to the Maestre train station on the mainland, our train is scheduled to leave at 7 a.m. and 1 person is flying out of Marco Polo airport and their flight departs at 8 a.m.. What is the best form of transportation from hotel to rail and airport?
Vapparetto will take to to the main train station. The Venice-Mestre Train Station is located on the Italian mainland, directly across the channel from Venice Italy. A shuttle train service connects Venice-Mestre to Venice's other train station (Santa Lucia) which is located on the Island of Venice. Train service between the two stations run several times per hour. For the aiport is it best to take a water taxi it is the quickest way to the airport. You may even be able to one water taxi driop you off at the train station and them off at the airport or vice versa
This is fairly easy to do, although you'll have to do your homework beforehand to check the boat schedules. From San Marco, you can take a vaporetto (water bus) or a water taxi to the Ferrovia station and then catch a train at Santa Lucia. It's a good sized train station, and all trains stop in Maestre. It's about a 5 minute train ride. I'm sure your hotel can help you determine which vaporetto line and time to use. To access the airport, the Alilaguna water boat service is the fastest option. Check out their website for fees and schedules. Have fun! It's a wonderful city.
For first timers I would suggest staying together as long as possible. That would mean taking the vaporetto to the SL train station and the train to Mestre. There is an airport bus that leaves from Mestre. You can see the schedule here: http://www.atvo.it/images_doc/linee/M.polo-Mestre_FS_(dal_1_al_12.09.2010).pdf