The arsenic (As) content of coal relating with mineralization of gold in Southwest Guizhou Province, China is up to 35,000 ppm. The coal is burned indoors in open pits for daily cooking and crop drying. As a result, arsenic is precipitated and concentrated in corn (5-20 ppm), chili (100-800 ppm) and other foods. Arsenic concentrations in the drinking water of high-As coal areas are lower than 50 ppb. The estimated main sources of As exposure in this area are from polluted food. Approximately, 3000 arsenosis patients were found by 1998, and more than 100,000 people from six counties were under the threat in China. This paper presents the major ingestion pathway of this type arsenosis and relative geochemistry of high-As coal.