<p>The destruction and dissolution of active functional groups in coal by ionic liquids (ILs) could effectively inhibit coal spontaneous combustion (CSC). However, high cost is a key factor restricting its widespread practice apply. So, four types of imidazolium ILs [EMIM]BF₄, [BMIM]I, [BMIM]BF₄, and [BMIM]NO₃ were specifically selected and mixed with H₂O₂ at a ratio of 1:1 with a concentration of 5.0% to treat coal in this work. Subsequently, the thermogravimetric process, kinetic characteristics, and combustion index of coal oxidation macroscopic were explored. The results show that thermogravimetric and the molecular activity decreases in coal treated with ILs and H₂O₂ during five stages and the mass gain appear significant. At the same time, the increase in critical temperature, active temperature, and mass maximum—increased rate temperature of coal, revealed the synergistic effect of ILs and H₂O₂ in inhibiting the chemical adsorption capacity of coal surface. This comprehensive effect resulted in a 15.1&#xa0;°C increase in the ignition temperature of CSC. The apparent activation energy (<i>E</i>_a) of coal single treated with H₂O₂ and ILs oxidized increased by an average of 118670.0&#xa0;J&#xa0;mol⁻¹, whereas the <i>E</i>_a of ILs and H₂O₂ increased by an average of 2425.0&#xa0;J&#xa0;mol⁻¹ when compared with single component liquid. Combined with the combustion characteristic evaluation index, the average reduction reaches 0.2e⁻⁸%&#xa0;min⁻¹&#xa0;K⁻³, which shows outstanding inhibitory effects. All the experimental results showed that the addition of ILS into H₂O₂ inhibition of CSC was caused by an enhanced oxidation of organic structure in H₂O₂ due to destruction of hydrogen-bonding networks and dissolution of small molecular structures of coal in ILs. The results contribute to provide a positive guide for the promotion and field application of ILs and H₂O₂ mixed solution in preventing CSC.</p>