Sulfur-containing groups (SCG) may be an essential factor influencing the spontaneous combustion of oil tank corrosion products and triggering fire and explosion accidents. The effect of three SCG on the spontaneous combustion susceptibility of model compounds of tank corrosion products (MCTCP) were investigated. The results show that SCG causes the surface of MCTCP to produce cracks and become rough, which adsorbs more oxygen and SCG, enhancing its spontaneous combustion susceptibility. After the SCG addition, the MCTCP thermal susceptibility partial indicator values decreased. The apparent activation energy and the flammable volatile compound release temperature decreased significantly, which increased the spontaneous combustion susceptibility of MCTCP. In addition, SCG also increased the number of exothermic peaks in the self-ignition process of MCTCP. The exothermic peaks partly came from the oxidation of SCG, and the heat generated by the oxidation of SCG increased the spontaneous combustion susceptibility. Therefore, SCG may affect the spontaneous combustion susceptibility through three pathways: changing the microform and structure of MCTCP, thermal susceptibility parameters, and oxidative exothermic properties. The work assists in deepening the theory of the mechanism and influence factors of spontaneous combustion of corrosion products in oil tanks, and provide guidance for the prevention of such accidents.