We spent 2 nights at the Hotel Rural Picos de Europa and had a wonderful stay. It's located in a beautiful position, 5 - 10 minutes walk from the village and there's plenty of parking space. The hotel is simply but very comfortably furnished, our room was excellent, but be aware you may have to carry bags up a couple of flights of stairs. Breakfast was simple, plentiful and beautifully presented - fresh orange juice, freshly made scrambled eggs, toast and jam and coffee. They don't do other meals, but it was a pleasant stroll to the village for dinner. Isabel and her husband (I don't know his name) were delightful hosts and extremely helpful. As we don't speak Spanish, we couldn't have in depth conversations, but Isabel spoke enough English so we could communicate. It didn't need English for her husband to set up a telescope and point out deer, chamois and climbers on the mountains from the comfort of the lounge!
When we left, I left a package behind in our room. We phoned to see if it could be forwarded to us, and when Isabel heard that we'd be in Madrid some weeks later and so would she, she went out of her way to deliver the package to our accommodation there. Definitely recommend staying here.