In the gas extraction and utilization process of coal mines, gas (mainly containing methane) explosion accidents happen occasionally under high-temperature conditions, causing serious casualties and economic losses. To reveal the mechanism and risk evolution of methane explosion under high-temperature conditions and control such accidents, the explosive characteristics of methane at 25∼200 °C were experimentally investigated by establishing a test platform for gas explosion under hightemperature conditions. In the experiments, three conditions were considered: the concentration near the upper explosion limit (CNUEL) (15.47 vol %), stoichiometric concentration (SC), and concentration near the lower explosion limit (4.68 vol %). Furthermore, the explosion pressure of methane−air mixtures and sensitivity characteristics of key free radicals at different high temperatures were determined based on the GRI-Mech 3.0 reaction mechanism of methane and using software CHEMKIN-PRO. The results show that at SC, P max decreases, while (DP/DT) max remains unchanged as the temperature increases, indicating a gradual decrease in the explosion risk. Near the explosion limits, P max and (DP/DT) max both grow as an exponential function, which implies that the explosion risk gradually increases. The temperature rise exerts a greater effect in improving the risk of explosion overpressure of methane at CNUEL (15.47 vol %), and compared with P max , the temperature rise has a greater improvement effect on (DP/DT) max . In the early stage of consuming methane, methane at SC mainly has two chemical reaction paths: CH 4 → CH 3 → CH 3 O → CH 2 O → HCO → CO and CH 4 → CH 3 → HCO → CO. The former and the latter to some extent separately promote and inhibit the explosive reactions. As the temperature increases, the proportion of methane consumed by the former reduces, while that by the latter slightly increases. The temperature rise inhibits the increase in the explosion risk of methane at SC, which is consistent with the experimental results.