Coal samples from high arsenic coal areas have been analyzed by electron microprobe analyzer (EMPA), scanning electron microscopy with an energy dispersive X-ray analyzer (SEM-EDX), X-ray diffraction analysis (XRD), low temperature ashing (LTA), transmission electron microscopy (TEM), X-ray absorption fine structure (XAFS), instrument neutron activation analysis (INAA) and wet chemical analysis. Although some As-bearing minerals such as pyrite, arsenopyrite, realgar (?), As-bearing sulfate, and As-bearing clays are found in the high arsenic coals, their contents do not account for the abundance of arsenic in the some coals. Analysis of the coal indicates that arsenic exists mainly in the form of As5+ and As3+, combined with compounds in the organic matrix. The occurrence of such exceptionally high arsenic contents in coal and the fact that the arsenic is dominantly organically associated are unique observations. The modes of occurrence of arsenic in high As-coals are discussed.