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Do you mean a boat trip on the canals of Livorno (which is the port for Florence)? That's probably the best way to see Livorno. But if you mean a trip on the canals of Florence, I would think a walking tour of the city would be far better.
My suggestion in any port is barter with the local taxi's outside the ports tell them u want 1 2 or 3 hours how much you will find they take you any where you like. at great prices we do this and seem to find they are great and they will take your picture as well and give you the local history.