The CO2 enhanced coal bed methane recovery technology provides an excellent way to mitigate the greenhouse effect and energy crisis. The features and mechanism of CO2/CH4 competitive adsorption in the coal rock matrix have a critical impact on the production of CBM. For CO2/CH4 competitive adsorption process components and pressure changes, a multi-component gases competitive adsorption experiment was carried out with CO2 and CH4 binary gases as the study objects, and a multi-component adsorption model was developed by the expanded Langmuir equation. Based on the principles of molecular dynamics and thermodynamics, important parameters such as the average free range of gas molecules and adsorption potential are introduced to explain the competitive adsorption behavior from multiple perspectives and explore the competitive adsorption law of CH4 and CO2 under multiple component conditions, so as to provide some theoretical basis and field guidance for improving the extraction effect of CH4 in coal seams. The results show that: Under two critical conditions (100%CO2 +0%CH4 and 0%CO2 +100%CH4), the Langmuir volumes of CO2 for HN 1/3 coking coal and HL weakly caking coal respectively are 2.21 and 3.01 times higher than those of CH4; the overall adsorption capacity of binary gas is in between the adsorption capacities of both critical conditions and increases with increasing CO2 concentration in the gas source ratio; using E-L equation for binary gas component partitioning, the CH4 partition curves were all below CO2, the concentration of free-phase CH4 was always higher than that in the adsorbed phase, and coal samples had stronger adsorption ability for CO2 than CH4. CO2 has a stronger adsorption potential at the surface for HL weakly caking coal. CH4 has a slightly stronger adsorption potential at the surface for HN 1/3 coking coal. The higher coalification degree of the coal sample, the stronger the adsorption ability for CH4 and the weaker the adsorption ability for CO2. The slope of the overall adsorption curve of multi-component gases is analogous to the slope of the component with a high ratio of gas or strong adsorption capacity; the capacity of one-component adsorption for dual gas is closely related to the partial pressure of the free-phase gas and the separation factor α21. When the concentration ratio of CH4/CO2 in free phase is y2/y1 =α21, the concentration of both gases in adsorption phase is 50%, and α21 correlation is weakened, then the free phase gas partial pressure is dominant and there is a threshold value makes CH4 and CO2 adsorption capacity equal; when y2/y1 <α21, the coal preferentially adsorbs CO2 in the binary gas; when y2/y1 >α21, the coal preferentially adsorbs CH4 in the binary gas.