If you need a hotel within walking distance to the the train station (Livorno centro is quite far from the station), Hotel Stazione is adequate.
On the plus side: the hotel is clean and it is close to the station, if that is important to you.
Otherwise, I'd put it around the level of a U.S. Motel 6: spartan (there really isn't any part of the hotel that is attractive), generic, uncomfortable, and unappealing furniture, no kettle/coffee/tea in the room, tiny plastic disposable glasses, small computer-sized TV monitor atop the "desk," and quite desolate at night.
My take is that you don't get much at all for €100/night but, again, it is convenient (and clean) if you need a hotel near the train station.
I don't think it's a hotel to which you'd be dying to return; it does its job, albeit minimally.