Here is the amount of time it will take to get to Venice by train from nearby towns and major cities; for the faster times on high-speed/EuroStar (ES) trains, expect to pay a bit more:
First thing you need to know: do not get off the train when it pulls into Venezia-Mestre.
This is the station for Venice's landlubbing industrial suburb of Mestre, a place you don't ever want to have to set foot in if you don't have to. (No, it's not dangerous, just exceedingly dull.)
Most trains will continue on from Mestre, across the causeway over the lagoon, and into Venice proper and the Venezia-Santa Lucia train station. This is where you get off.
(Note: Some high-speed trains skimming past Venice will, indeed, stop only at Mestre. If this happens—or you accidentally get off in Mestre—never fear. There are trains making the short, five-minute hop to Venezia-Santa Lucia every 10 to 15 minutes or so).
Inside the station, there's a deposito bagagli (left luggage/bag storage) facility by binario (track) 14, on the far left as you're walking from a train toward the ticketing hall; the public bathrooms are nearby.
In the train station's main atrium, just to the right of the left-hand exit doors as you're leaving, is a tiny, crowded tourist information office (tel. +39-041-529-8727; open 8am–6:30pm) and, right next to it, a hotel booking office (tel. +39-041-522-2264; open 8am–9pm).
Do not get these two offices confused. After years of dealing with lost tourists who constantly ask one office for information more appropriate to the other—for example, showing up at tourist info wanting to book a hotel, or at the hotel booth asking for a map of the city and list of open hours for museums—the staffs of these two tiny offices seem to have grown to hate each other (or perhaps just the tourists) and tend to be quite snippy about forcing you to go to the other office for your intel—and, typically, wait in another long line. Make sure you get in the correct line!
That church across the way
That church directly across the Grand Canal from the station with the green oxidized dome and Neoclassical facade is the 18th century San Simeon Piccolo. It's rather unimportant as far as Venice churches go, but it's most people's first view of Venice—and, if you've a long wait for your train, the one you stare at longest. Closed for what seems like decades, it has recently reopened, and holds the quirky status as the only church in Venice celebrating Mass in Latin daily (Mon–Sat at 8am; in Gregorian chant Sun at 11am). » more
Exit the train station and directly in front of you is the famous Grand Canal, Venice's watery Main Street. Look to your left and you'll see a pair of floating docks for the vaporetto (public ferries, Venice's public "bus" system).
The dock off to your right (S. Lucia) handles Lines 1 (local down the Grand Canal), 4.1 and 4.2, and 5.1 and 5.2.
The dock off to the left (Scalzi, just before the big bridge) handles line 2 (express down the Grand Canal) and the N (the night ferry).
Go to the dock of your choice, buy a ticket from the booth (yes, it really costs €7; they're not trying to scam you—well, they kinda are, but it's the city of Venice doing it, not the guy at the booth), and hop on the no. 1 (local) or no. 2 (express) line headed left, which is downstream, as it were, chugging down the Grand Canal toward the Rialto bridge and, eventually, Piazza San Marco. » more
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