Bolivia travels best in legs rather than loops, because the altitude decides the pace. The altiplano in the west carries La Paz, Lake Titicaca and the salt flat at Uyuni, and most itineraries build in a few days to acclimatise before attempting any of it. The central valleys are the gentler half: Sucre and Cochabamba sit lower, warmer and greener, which is why Sucre is where people stop to learn Spanish. East of the Andes the land drops into the Amazon basin and the Chiquitania, a different country in everything but the paperwork.
1 Bolivia city guide
Fun fact
Bolivia has two capitals. Sucre is the constitutional capital and keeps the Supreme Court; La Paz has held the government and the legislature since 1899, after a civil war settled the argument.
