Coal for CO₂ adsorption ability was strong, coal was preferentially adsorbed by CO₂, which reduced the amount of O₂ adsorption and inhibited the process of coal adsorption oxygen, the coal had strong adsorption ability to CO₂. Through carrying out temperature-programmed experiment, the inhibition that CO₂ affecting the process of coal adsorption oxygen was studied, the concentration values of O₂, CO, CH₄ that coal samples produced at different concentrations of CO₂ were measured, and the discipline that CO₂ concentration influencing on consumption rate of oxygen and production rate of CO were analyzed. The results showed that, when the concentration of CO₂ was 37%~50%, it had a significantly inhibitory effect on the consumption rate of oxygen in the process of coal oxidation, and decreased the ratio that the amount of releasing CO changing with temperature. CO₂ can effectively inhibit the process of coal adsorption oxygen, and prevent the occurrence of spontaneous combustion of coal. The results of this experiment had guidance significance for the development and application of fire prevention technology on CO₂.