Carbon dioxide (CO2) is widely used in the prevention and control of spontaneous coal 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 the competitive adsorption of CO2 and oxygen (O2) in coal pores, and simulation study of the CO2 inhibition of the coal oxygen composite reaction were used to obtain the role and effect of CO2 in preventing oxygen adsorption in coal at the low-temperature oxidation stage. It was concluded that CO2 can displace the O2 near the pore wall to physically prevent the adsorption of O2. Through the changing law of heating rate and a kinetics analysis, it was found that CO2 can increase its activation energy by 5.3−108.3% during the slow heating stage of coal and reduce its heat rate. At around 120 °C, coal loses the protective effect of CO2. From the changes in functional groups, it can be seen that when coal was cooled in the CO2 atmosphere, mainly pyrolysis and condensation reactions occurred due to the lack of O2. In addition, CO2 can also inhibit the chain reaction of the chemical adsorption of oxygen in coal. This work provides a theoretical basis for CO2 prevention and the control of spontaneous coal combustion.