Free radicals and metal ions are key factors causing coal spontaneous combustion. In order to effectively suppress coal spontaneous combustion, experiments were conducted using luteolin as an inhibitor, luteolin is abbreviated as LUT. The influence of different concentrations of LUT on the spontaneous combustion heat characteristics of coal was tested using a C600 high-precision microcalorimeter, and the inhibition mechanism was inferred by FTIR. The experimental results show that LUT is an effective coal oxygen inhibitor, under the same action conditions, different concentrations of LUT can absorb heat to different degrees, delay the initial exothermic temperature of coal, prolong the heat absorption phase of coal. Compared with raw coal, 6 wt% LUT absorbs the most heat, the starting exothermic temperature is delayed by 46°C, and the activation energy is increased by 47.89 kJ/mol, the functional group -OH content decreased by 43.4%, -CH3 decreased by 32.1%, -CH2-decreased by 37.76%. Based on this, the mechanism of inhibition is inferred, LUT not only removes free radicals (ROO•) during the chain initiation stage and captures free radicals (•OH) in the reaction chain but also chelates metal ions to inhibit the catalytic effect of metal ions during the free radical reaction, which can play a dual role in preventing free radical generation and interrupting the free radical chain reaction. The results of the study can provide a novel, environmentally friendly and effective way to prevent the spontaneous combustion of coal.