It was acquired in the 1900s by Simón Iturri Patiño, who was dubbed the "King of Tin." It was the site of continual labor strife, and many of its workers were active in the Union Federation of Bolivian Mine Workers (FSTMB).
During a labor dispute between miners and management in December 1942, the striking miners at Patiño's Catavi mine were massacred by government troops in the Catavi Massacre. The mine was nationalized following the "Bolivian National Revolution" of 1952, when the Revolutionary Nationalist Movement (MNR) and its allies overthrew the military junta. Catavi and other mines were placed under the control of a new state agency, the Corporación Minera de Bolivia (COMIBOL). The Catavi-Siglo XX complex became the largest component of COMIBOL, employing some 5,000 workers.
On June 24, 1967, government troops under the orders of General René Barrientos and a new military junta marched on the mine and committed the largest massacre of workers in Bolivian history. The massacre occurred on St John the Baptist's Day, an indigenous holiday.
Over the following decades, the tin deposits in the mine become exhausted. In 1987, as part of an economic restructuring deal with the IMF and World Bank, the government shut down production at Catavi.
- Klein, Herbert S. (1971). "Prelude to the Revolution". In James Malloy and Richard Thom (eds.), Beyond the Revolution: Bolivia Since 1952. Pittsburgh: University of Pittsburgh Press, pp. 25–52. ISBN 978-0-8229-3220-8.
- Nash, June (1993). We Eat the Mines and the Mines Eat Us: Dependency and Exploitation in Bolivian Tin Mines. New York: Columbia University Press. ISBN 0-231-08050-6, ISBN 0-231-08051-4.
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