Though I too usually stay in albergues, over the years I've had my fair share of splurges.
Castrojeriz: La Posada de Castrojeriz,
http://www.laposadadecastrojeriz.es/ (but as I was looking it up on google, I came across another one that looks nice and maybe a little less expensive since it's a ** rather than a ***, Hotel La Cachava,
http://www.lacachava.com/ )
Villalcazar de Sirga, Hotel Infanta Dona Leonor,http://www.hostal-infantaleonor.com/ . This is a one star hotel, and when I stayed there about 5 years ago, it was immaculate. It's newly built, centrally located, and has a nice garden out back. There is a church in town with a wow-zer retablo (not sure what that's called in English), and a very good restaurant if you're into meats. Also various bakeries with local specialties.
Carrion de los Condes. The Santa Clara Convent right at the entrance to town has private rooms, and is very clean. I have stayed there twice, and was always put in a triple room, but I imagine that they have other sizes as well. I have a vivid memory of crisp brilliantly white sheets, which were a welcome change. But I have also stayed at a three-star hotel on the Camino on the way out of town, located in an old monastery, The Hotel Monasterio San Zoilo,
http://www.sanzoilo.com/. As guests there we had free run of the church/cloister, etc, which was quite a treat. The grounds were also great for picnics. I think I may have read something about renovations, but their website just shows that they are closed from the 24th of Dec. to 6 Jan. I also once heard from someone who got bedbugs there, or thinks he did, but I know that can happen anywhere on the Camino.
In Leon,I frequently have a little splurge and stay at the Posada Regia. It's an old stone building, terrific location, and very nice staff.
http://www.regialeon.com/
Buen camino, Laurie