You can purchase tickets at any city's (bus stations
) (known as 'Terminal de Buses') except in Santa Cruz, where the bus station is called the 'Terminal Bimodal' (dual bus and train station) from which all intercity and interstate buses depart. From here you can go to practically any other city in the country including La Paz, Cochabamba, Oruro, Sucre, Potosí, Trinidad, Tarija, Puerto Suarez, and all points in between. Bus tickets must be paid in cash and, with few exceptions, most bus companies don't sell tickets in advance. Those that do, will usually sell bus tickets only one day prior to travel.
Bus tickets can be bought in person at the window of the 'flota' company you plan to use. Don't buy from ticket 'scalpers' (resellers) who loiter around the terminal. Prices may be cheaper, but tickets may be useless.
Alternatively, you can buy bus tickets, see their routes, and find distances between cities, online with a credit card at www.ticketsbolivia.com, where you can also buy tickets for Bolivia's trains.
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YOU CAN BOOK FLIGHTS TO BOLIVIA ON THESE TRUSTED TRAVEL SITES