If you're looking to walk the Cinque Terre we'd happily recommend that you stay in La Spezia at the Hotel Astoria. The staff are friendly and the rooms are comfortable- which is just as well if you intend on nailing all 5 villages in one go. The hotel is only an 8 min walk from the train station, which can take you out of town or to the start of the Cinque Terre. Better still the hotel is about 2 mins walk from a variety of Piazza's where good food and wine can be found. Throw in the fact that the breakfasts are great and i can't speak highly enough of this place given its value for money.

Positive:

-location (near center and central rail station)
-very clean and quite rooms
-good breakfast (good coffee)

Negotive:

-no WiFi connection at all

I was unexpectedly in La Spezia and needed a hotel for the night. Found this in my Rick Steves guidebook and it was reasonable priced and about 2 blocks from the train station.
We checked in after midnight and the staff was still very friendly. Got a room for two people with a private bathroom. Room had cool tile floors and a balcony with a great view. Although the room was rather plain it was clean with comfy beds. Breakfast was included but we slept though it and they even let us have a late check out.

My girlfriends and I found this hotel off a website we had been using on our Europe Holiday. From the pictures on this website is looked fantastic - white, clean and beautfully presented. Unfortunately the room we got was a tad old and needed a refurbishment. It was clean and the beds were rather comfortable but the bathroom is definitely in a need of fixing. Water pressure was just a dribble and the toilet made a very strange and loud sound when you flushed it. BUT would have to say that the breakfast was impressive - loads of choice and freshly made coffee. Staff seemed friendly at first but got the 'cold-shoulder' not long after. This hotel was definitely an experience and we can have a laugh about it now!