Southern France has tons of beautiful routes in the mountains, on both sides of the Rhone River. Buy the Michelin Southern France map and follow virtually any of the green labeled routes and you will not fail to find fantastic countryside, small quaint stone villages and great vistas. I drive through Southern France everytime I leave/return to homeport (Barcelona) and head to northern/ eastern europe or Asia for overlanding and never cease to be amazed with the beauty I find there. The river Valleys like Lot River are especially beautiful, but then hell, so are the mountain tops. Just drive the green routes and you will not go wrong.
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