A wonderful ride up the road from Potes is Fuente De. There you can find a Paradore and the Hotel Rebeco.
http://hotelrebeco.com/?lang=enStayed there in the summer of 2011 with a group of friends on bikes. It's your standard Spanish hotel with decent rustic food and clean rooms. I would happily stay there again. There's a small garage where they will let guests park bikes if desired.
An advantage of staying here is that you have to ride the road to Potes twice every day you go out. Even better, as you leave in the mornings the roads going down the valley are quiet, as folks tend to visit Fuente De from Potes and beyond. The reverse is true in the afternoon.