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Although the highways aren't the best, driving can be a nice way to see some areas of southern Bolivia. When visiting Potosí it's best to fly to Sucre and drive from there. You should also consider hiring a car and driver or taking a tour through a travel agency. The highway is good between Sucre and Potosí, but plan to overnight, as it passes through mountains and is not lighted. The best way to get to the wine country of Tarija is by flying direct from La Paz or Santa Cruz.