Two different rank coals with high organic sulfur content were selected and pretreated with tetrachloroethylene (PCE) under ultrasonic field. The effects of pretreating process on sulfur forms in two coals have been investigated by chemical analysis and sulfur K-edge X-ray absorption spectroscopy (S-XAS). The transformation behaviors of sulfur forms during pyrolysis of raw and PCE-treated coals in the fixed bed reactor with temperature-programmed apparatus were studied by gas chromatography (GC) and S-XAS. Results show that sulfur removal degree of Coal A and Coal D are 29.7% and 24.1%, respectively; and the removal of organic sulfur are dominant, accounting for 87.1% and 66.1% of total removal of sulfur from Coal A and Coal D. The sulfur compositions in coals obviously change before and after PCE extraction, and these changes appear to be unevenly distributed on the surface and in the bulk of coal. The effects of PCE extraction on the release of sulfur-containing gases are different for two coals, which are dependent on the sulfur forms in the coals, as well as the chemical structure in coals. The sulfur forms retained in the chars are significantly different for low rank Coal A before and after PCE extraction, but there is little change for high rank Coal D. (C) 2016 Elsevier Ltd. All rights reserved.