Though not included on the standard tours, there is plenty of scope for hiring your own driver and climbing some volcanoes. Guides are easy to find in the region’s settlements or can be organised through a tour company in Uyuni. The challenging aspect of most of the climbs is the altitude rather than technical difficulty.
The most frequently climbed is Volcán Licancabur (5960m); it takes about eight hours to climb to the summit and two to get down. Several Uyuni and Tupiza agencies can include a guided climb of the volcano in a Southwest Circuit route, adding an extra day to the trip. You can normally find a guide near the campsite in Laguna Blanca – they tend to charge about B$500 for an ascent of the mountain, which has a beautiful lagoon at the top. The climb can be done comfortably (if you handle the altitude) in one day. As the volcano is sacred to the locals, the guides usually perform a ritual for Pachamama, asking the earth goddess for her permission to climb.
Nevado Candelaria (5995m), southwest of Salar de Coipasa, is also an exhilarating climb. The active Volcán Ollagüe (5865m) on the Chilean border southwest of San Pedro de Quemez is another interesting option, with spectacular views.
A rounded promontory juts into Salar de Uyuni diagonally opposite Colchani, and on it rises Volcán Tunupa (5432m), which you can approach from the village of Coquesa (10 hours there and back, including a visit to the caves that house pre-Incan mummies). Local guides charge around B$500. Altitude aside, this hulking yellow mountain is a relatively easy climb. One legend linking it to the origins of the salt flat states that 16th-century Inca ruler Atahualpa slashed the breast of a woman called Tunupa on the mountain's slopes, and the milk that spilled out formed the salar. Another story tells that in ancient days, mountains were men and women. Right after giving birth to their baby, Tunupa learned her man was living with another woman. Devastated, she wept and wept, spilling her salty tears over her breast milk and creating this vast area of sadness and beauty that is now the salar.
It’s also possible to climb Uturuncu (6020m), which is an active volcano; jeeps can drive up to 4800m, from where you can hike to the top – an easy way to say you’ve climbed a 6000m-high volcano!