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Burkina Faso, formerly Upper Volta, is a landlocked country in West Africa. It is surrounded by six countries: Mali to the north, Niger to the east, Benin to the south east, Togo and Ghana to the south, and Côte d'Ivoire to the south west. Many experienced travellers consider Burkina Faso to be one of the most friendly and inviting countries in Africa. However Burkina Faso is also a very poor country. The official language is French but other languages are spoken more widely, knowledge of Bambara can be useful.
It is by all means possible to hitchhike in Burkina Faso, but naturally the experience is pretty different from the one you might have in Europe, North Africa or the Middle East. In Burkina Faso the majority of people who travel do so by bus and there are few cars on the road. However, it won't take to many of the sparse cars passing before someone will stop, usually curious as to why you are standing by the road with your thumb or finger out. When the situation is explained, more often than not, the driver will be happy to help out a traveller and will probably be excited to meet you!
As with hitching in general, it is better to be outside of the bigger cities, mainly because you will attract a lot of taxis. Getting out of the two sprawling bigger cities (Bobo Dialasso and Ouagadougou) can be a bit of a mission on foot, so it might be worth taking a shared taxi or bus (in Ouaga) a little way along the road. As a traveller, you may be in for some hassle if you stroll past the 10 or 20 bus companies and stations that line the exits of the cities, as they'll wonder why you are walking (and saying "I fancy hitching", even in French) probably won't satisfy them.
A word of warning. Whilst hitching in many countries is a great way to get to the underbelly of a culture and experience some hospitality, in Burkina Faso car drivers tend to be businessmen with a business reason for their trip or or other travellers. (Not to say that both of those won't be wonderful, interesting, generous people but rather that you might not get the random cross section of society that you're used to).
The biggest roads in Burkina are generally pretty well maintained, promptly repaired after the rainy season, particularly the route between Bobo-Dialaso and Ouagadougou.
Most Burkinabe you encounter will speak at least some French and some people will speak English.
While hitching in Burkina, hitchwiki user jim_e99 did not receive any offers of a place to stay, in about 6 lifts. It is probably worth asking people, because hospitality is pretty engrained in Burkinabe culture. Alternatively, several great Couchsurfers exist in Ouagadougou and a handful in Bobo. On the other hand, during one month of moving through various parts of the country, Alyssa was often offered a place to sleep, both by drivers of hitched rides and while walking through villages. In all cases the people were well intentioned and happy to help out a foreigner.
In 2010 the price for buying the Burkinabe visa at the border went from 10,000 CFA to 100,000 CFA, so best to get it before hand - it is a straightforward 24-hour process at the embassy in Bamako, and they will likely grant you three months for the price of one.
If you plan on traveling to other West African countries, Ouagadougou is a good place to pick up the 5-country Visa Touristique Entente, good for a single entry into each of Burkina, Cote D'Ivoire, Togo, Benin and Niger. The visa starts on the day you use it and lasts two months, for a price of 25,000 CFA (a one-month visa to Cote D'Ivoire is a bureaucratic pain to get and costs 8,000 CFA more). You must go to the Direction du Controle de la Migration, as most embassies will deny its existence (for example the Ivorienne embassy claims it no longer works). This information is from late 2010, play around on Google to get the latest.
Similar situation for most West African countries. Rides come quickly and most people are well intentioned. Single women, keep your wits about you, but definitely possible to hitch without problem. The only potential issue is the recent activity of Al Qaeda in Islamic Magreb in the north-eastern parts of the country, notably near the Mali and Burkina borders. Stay informed about the situation.