Abstract: To explore the influence of sulfur content on the spontaneous combustion characteristics of coal and find efficient ways to prevent and control the spontaneous combustion disaster of high sulfur coal, the oxidation processes of typical high sulfur coal and typical low sulfur coal were analyzed using a comprehensive thermal analyzer (TG/DSC) and a programmed heating experimental system. The complexation of commonly used inhibitors, Ca(OH)₂, Na₂CO₃, MgCl₂ and two typical organic sulfur structures, diphenyl sulfide (C₁₂H₁₀S) and benzenethiol (C₆H₅SH), in high sulfur coal and coal were calculated using quantum chemistry simulation software. The results showed that the mass loss rate during the oxidation process of high sulfur coal was faster, and the heat release was greater. The activation energies of high sulfur coal in the pyrolysis and combustion stages were 9.16% and 15.07% lower than those of low sulfur coal, respectively, indicating a higher tendency to spontaneous combustion. Na⁺, Mg²⁺, Ca²⁺ in the commonly used inhibitors in coal mines can form complexes with diphenyl sulfide and benzenethiol, and the chemical reactivity of the two organic sulfur structures decreases after forming complexes, which can inhibit the spontaneous combustion of coal.