He was received by Bolivia’s first indigenous leader, President Evo Morales, who gave him a ritual pouch with coca, a sacred leaf in the Andes.
Pope Francis insisted that the Catholic Church should continue to play an important role, to protect the most vulnerable in society from the impact of capitalism.
He also called for dialogue between Bolivia and Chile over their long-time border dispute.
The Pope was said to have flown in from Ecuador and will also visit Paraguay.
The Pontiff hailed Bolivia for encouraging the poor to be active citizens, saying ”Bolivia is making important steps towards including broad sectors in the country’s economic, social and political life”.