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The city of Sucre is not large, and many of the historic attractions can be seen on foot. Many of the museums and other attractions are close together, so walking is a good option. There are numerous buses and these can be crowded, but not terribly so except during the morning and evening rush hours. If you can avoid traveling at these times the bus is certainly the way to go, but watch your possessions as petty crimes, including bag snatchings are rampant on the buses.
Taxicabs are a good alternative, but the city has begun to warn tourists not to take random cabs. But sure to look for a licensed cab only, as other semi-legal and gray-market drivers charge a much higher than normal rate. Likewise, kidnappings remain a problem in parts of Bolivia, and one method is to take tourists for a true ride of their lives.
Rental cars are also available, but the road conditions outside of the city can range from poor to downright awful. It isn’t uncommon to find unpaved roads, and be sure to watch for wildlife and livestock as well.