CO2 is widely used in the prevention and control of coal spontaneous combustion. In this manuscript, three low-rank coals with different metamorphic degrees were selected as the research objects. The temperature-programmed experiments, in-situ infrared cooling experiments, simulation of competitive adsorption of CO2 and O2 in coal pores, and simulation study of CO2 inhibition of coal oxygen composite reaction were used to obtain the role and effect of CO2 in preventing oxygen adsorption in coal at low-temperature oxidation stage. It is concluded that CO2 can displace the O2 near the pore wall to physically prevent the adsorption of O2. Through the change law of heating rate and kinetic analysis, it is found that CO2 can increase its activation energy by 5.3%-108.3% during the slow heating stage of coal, and reduce its heating rate. At around 120°C, coal loses the protective effect of CO2. From the changes of functional groups, it can be seen that when coal is cooled in CO2 atmosphere, mainly pyrolysis and condensation reactions occur due to the lack of O2. In addition, CO2 can also inhibit the chain reaction of coal's chemical adsorption of oxygen. This work provides a theoretical basis for CO2 prevention and control of coal spontaneous combustion.