Abstract: The effects of different Fe, Cr and Mn additives on the desulfurization of coking coal with high sulfur during coking process were investigated by crucible coke. Also, the effects of the additives on the desulfurization during coal pyrolysis and the evolution of sulfur-containing gases under different atmospheres were examined in a fixed bed reactor. The results indicate that the effects of additives on the sulfur forms of coal are different. Fe³⁺ which has an oxidability decreases the pyrite content of coal while other additives have little effect on the sulfur forms of coal. Chromium additives increase the desulfurization of coal pyrolysis, but iron and manganese additives decrease that during simulated coking process. The pyrolysis of Cr³⁺ loaded Jiexiu coal indicates that the desulfurization of coal with Cr³⁺ under N₂ is restrained and the evolution of sulfur-containing gases is decreased, and the unstable organic sulfurs are converted to stable organic sulfurs; on the other hand, the desulfurization of coal with Cr³⁺ is facilitated under reductive atmospheres and the yield of sulfur-containing gases is obviously increased. The effects of the simulated coke oven gas (SCOG) on the desulfurization of coal with additives and the evolution of sulfur-containing gases during pyrolysis are similar to those of H₂, so SCOG can be used as the reaction atmosphere for increasing the desulfurization during pyrolysis with transition metals additives.