One day can be enough for some folks, like me - been there thrice - each time for a day and day trip

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For a one night stay in le Cinque Terre it is better driving tours of ireland to book something that you can cancel on short notice if the weather turns rainy. There is little point in spending 3 hours on a train getting to le Cinque Terre, and then another 5 hours going to Venice from there if it is raining that day in le Cinque Terre.
Yes trains are the best way - from Florence there is an odd IC train that is faster driving tours of ireland and more expensive but goes direct I think to Monterosso, along with Riomaggiore the two Lands where mainline trains stop - shuttle trains trundle constantly between these towns and the other three towns - so buy a ticket from Florence SMN (Santa Maria Novella) station - the main in-town Florence station right to whichever driving tours of ireland of the 5 villages you want to end up in - mainly these are regional trains that demand a change or changes at:
Pisa Centrale and La Spezia Centrale - regional trains have a flat fare so there is absolutely driving tours of ireland no reason to book in advance - I do believe you cannot even make reservations driving tours of ireland if you wanted to and can always get on.
Now for CT to Venice yes booking in advance at www.trenitalia.com can get nifty discounts but those tickets are sold in limited numbers so much be booked for a specific train weeks in advance to guarantee availability then have restrictions on changes and refunds I believe.
Now getting www.trenitalia.com to work for discounted tickets (absolutely no reason to buy full-fare tickets until you get to Italy IME) i problematic for many novices but if you post on Fodor's "Help with Trenitalia Bookings" some experts like kybourbon (and others), driving tours of ireland the guru of making trenitalia.com work IME will kindly come to you aid.
To me the best part of the Cinque terre was taking the boat for a full day seeing the towns from the water and getting off at three of them. That would require minimum two night stay Otherwise I would not bother.
One day can be enough for some folks, like me - been there thrice - each time for a day and day tripping in - first time hiked the seven miles or so between all 5 villages - another time did a day trip from Florence and visited all 4 seaside villages by train - boat would be nice in season driving tours of ireland when they run.
PalenQ I think my wife and I can do the one day thrill. We defenatley would like to spend more time in the major cities Rome, Florence Venice...etc. And maybe we will do another trip to Italy and see the countryside; tuscan wine tours, Valle d Aosta, Amalfi coast ...and the not so touristy places.
I did train from Florence with a change in Pisa. Very easy. I would stay at least one night. We stayed a La Spezia which is a little larger and had nice hotels and places to eat. More to do at night. Ferry leaves from there or train.
You could have only one change of trains if you take a direct regional train from Monterosso to Milan then get a direct train to Venice driving tours of ireland - leave plenty of time however for changing in a humongous Milano Centrale station - not to worry you but zillions of tracks - all well-marked as to where that train on that platform is going but takes time to ferret out and trains can always be late.
Going back to Florence will be a snap since you will have come from there - a simple change in Pisa Centrale, a small enough station with just several platforms and again the info is all well marked - Florence to Venice SantaLucia (Venice SL in schedules) is by super comfy faster high-speed trains.