An integrated analytical approach has been used to determine the mode of occurrence of arsenic in samples of four widely used US coals: the Pittsburgh, Illinois #6, Elkhorn/Hazard, and Wyodak. Results from selective leaching, X-ray absorption fine structure (XAFS) spectroscopy, and electron microprobe analysis show that pyrite is the principal source of arsenic in the three bituminous coals, but the concentration of As in pyrite varies widely. The Wyodak sample contains very little pyrite; its arsenic appears to be primarily associated with organics, as As3+, or as arsenate. Significant (10-40%) fractions of arsenate, derived from pyrite oxidation, are also present in the three bituminous coal samples. This information is essential in developing predictive models for arsenic behavior during coal combustion and in other environmental settings.