Some of my favorites:
Monistrol d'Allier: Le Repos du Pèlerin. Physically a little run down, but the people there were very nice. They played music and sang, other guests played music and sang, I played flute. A great evening.
Mondenard: gîtes de Lesclapayrac about 3km off GR65, but lovely people. I was the only guest and ate in Jean-Claude and Danielle's kitchen with them. Between her staggering English and my staggering French, we had a nice dinner conversation!
Arblade-le-bas: Gîte Chambre d'hôtes Belardine. Another detour off GR65, but really no longer, it's an older version of the route. Helen Aitken an ex-pat Brit was very nice. Good food, English conversation!
Labalette: Gîte d'étape A Labalette. Nadine and Michel, a lovely retired farm couple. I was the only guest, the house has been in the family for several genarations.