Abstract: The oxidation characteristics of coal are significantly influenced by oxygen volume fraction and inertization treatment. To systematically analyze the combined effects of these two factors on coal oxidation behavior, programmed temperature rise experiments were conducted to analyze the gas generation patterns, oxygen consumption rate variations, and critical oxygen volume fraction for spontaneous combustion in raw and inertized coal under different oxygen volume fractions. The experimental results show that with increasing oxygen volume fraction, the intensity of coal oxidation reactions increases notably. At an oxygen volume fraction of 21%, the volume fraction of characteristic gases such as carbon monoxide and ethylene, as well as the oxygen consumption rate, rise sharply, indicating the highest oxidation intensity. Compared with raw coal, inertized coal exhibits significantly lower gas generation and slower temperature rise under the same condition, along with a reduced oxygen consumption rate, demonstrating the effectiveness of inhibitors in suppressing coal oxidation, particularly under low-oxygen condition. The critical oxygen volume fraction for spontaneous combustion to be approximately 8% for raw coal and around 12% for inertized coal, confirming that inertization can effectively delay the onset of intense oxidation and improve the resistance of coal to spontaneous combustion. Regarding indicator gases of spontaneous combustion, carbon monoxide remains the most reliable and sensitive predictor of coal oxidation, while ethylene, ethane, and propane serve as useful supplementary indicators. In contrast, methane is significantly affected by external conditions and geological occurrence, making it unreliable as an indicator gas for spontaneous combustion. In the raw coal area, it is recommended to control the volume fraction of oxygen below 8% to maximize the inhibition of oxidation reactions and reduce the risk of spontaneous combustion; in the inerting coal area, depending on the inerting effect, the volume fraction of oxygen can be controlled between 10% and 12% to ensure safety.