A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.