Lviv is a city in the West of Ukraine.
There's a good cheap train transportation system within Ukraine. There's no sense in hitch-hiking, unless you want to enjoy yourself dealing with locals.
Dentistry in Lviv is EXTREMELY cheap and EXTREMELY good. Since Europeans don't need a visa to Ukraine, if you are a penniless nomad and you have teeth problems, it makes sense to come to Lviv to replace the filling (or have some other more complicated treatment) :) it's ~15 eur per filling.