If you planing to backpack through Bolivia you most check my Bolivia backpacking itinerary, I logged all the key information you need to know about Bolivia.
I backpacked through Bolivia around June 2016.Bolivia is a great country and one of the cheapest you will find in south america. Unfortunately I only had 7 days in Bolivia, and i did not cover some city, the reasons being I meet great people on my 3 day tour in salar de uyuni and we decided to travel together for some time. Hence instead of me going to Santa cruz and Sucre I ended going to San Pedro which was great. I might go back to Bolivia when I do Argentina. However my main objective in Bolivia was to see La Paz and Salar de uyuni, which i happily did.
I talked all about my Bolivia trip in here. I will talk more about the country in here. The cites in Bolivia is reasonably well connected by buses. I found it very easy to move from one city to another. From my experience you can book bus on the same day, but its always good to check. Hence you can start you trip in Bolivia from any city you like depending on how you entering the country or were from. Many traveler including my self entered Bolivia from Pure through Copacabana.
You can start your tip in Bolivia