In order to develop appropriate desulfurization strategies, the organic sulfur species and their distribution in coal need to be characterized. Peroxyacetic acid oxidation has been developed to render coal soluble, allowing for the subsequent GC-FID/FPD and GC-MS analysis of sulfur compounds. Four Illinois Basin coals and samples of sporinite, vitrinite and semifusinite isolated from them have been examined. Between 20 and 50% of the organic sulfur in these coals is associated with relatively few compounds detected in the volatile oxidation products. Of these, methylsulfonic acid is the most abundant, which, from model compound studies, results from oxidation of either methyl disulfide or simple thiophene structures in the coals. Although the species detected are commonly occurring among the majority of the coal and maceral fractions, their distribution varies considerably from sample to sample. By fractionating the oxidation products, a fraction was obtained that had a sulfur content of 18%. This fraction represents nearly 50% of the total organic sulfur but only 10% of the weight of the coal. Using peroxyacetic acid to desulfurize coal, it has been demonstrated that all pyrite and sulfate can be removed at room temperature and at least 25% of the organic sulfur at slightly higher temperatures