In order to study the oxidation behavior induced the spontaneous combustion of accumulated pulverized coal during the process of its storage and transportation within an air leakage circumstance, during the oxidation and temperature increase, and to reveal the mechanism of [BMIM][BF4] ionic liquid inhibiting oxidation and flame retardant characteristics of pulverized coal. This paper used a high-efficiency inhibitor [BMIM][BF4] ionic liquid to inhibit the non-caking coal pulverized coal of Hongliu Coal Mine (HL), measuring the critical parameters of pulverized coal spontaneous combustion that treated by [BMIM][BF4] at 5%, 10%, 15% mass concentration, this is the minimum ignition temperature Tm and ignition delay time ti of pulverized coal, and analyzing the influence of [BMIM][BF4] on the heating and self-heating process of pulverized coal; testing the macroscopic resistance characteristics of [BMIM][BF4] to pulverized coal under the same high temperature circumstance (all pulverized coals were ignited). Furthermore, FT-IR experiment was used to characterize the microscopic resistance characteristics of pulverized coal by [BMIM][BF4] to verify the variation of the critical parameters during pulverized coal spontaneous combustion. The results show that [BMIM][BF4] can efficient inhibit the self-heating reaction of pulverized coal, increase the Tm and ti values of pulverized coal, reduce the risk of pulverized coal spontaneous combustion, and the higher its concentration, the greater the critical parameter of pulverized coal spontaneous combustion. Among them, Tm of coal powder treated by [BMIM][BF4] at the 15% mass concentration is 156 ℃, which is +26°C longer than the original pulverized coal redundancy, and the ti is 80 min, which is 32 min later than the original pulverized coal ignition. Under the same experimental temperature Ta (Ta＞Tm), the center point temperature, oxygen consumption rate, and CO production of pulverized coal that treated by the [BMIM][BF4] are all lower than the original pulverized coal, and the inhibition effect enhanced with the increase of the mass concentration of [BMIM][BF4]. Meanwhile, the inhibited effect of [BMIM][BF4] is reflected in the strong electronegative fluorine atoms forming strong hydrogen bonds with the hydroxyl hydrogen atoms in coal, dissolving and destroying the hydroxyl groups in the coal, and blocking the coal oxygen chain reaction.