Geological carbon storage, particularly within coal seams, is recognized as a viable strategy for achieving net-zero emissions. However, following CO₂ injection into the coal seam, limited studies have addressed the competitive sorption dynamics of CH₄ and CO₂ on coal, despite the natural presence of CH₄ in these formations. In this work, sorption experiments were conducted using two types of coal: sub-bituminous coal and anthracite. Initially, pure CH4 and CO2 gases were employed to conduct individual sorption tests. Subsequently, the competitive sorption of CH4 and CO2 was evaluated using pre-mixed binary gas mixtures with varying CH4/CO2 ratios. Further, the displacement effect of CO2 on CH4 was investigated by injecting CO2 into coal samples that had been pre-adsorbed with CH4. The data reveal that, for both coals, the ideal selectivity calculated from pure gas measurements underestimates the corresponding values from real multicomponent systems. Anthracite demonstrates a higher selectivity for CO₂ over CH₄ during both adsorption and desorption processes when compared to the ideal selectivity calculated from pure gas sorption data. Conversely, the sub-bituminous coal initially shows lower selectivity for CO₂ than for CH₄ during adsorption, but this trend reverses and intensifies during desorption. If competitive sorption effects are neglected, coal selectivity for CO₂ over CH₄ under the examined conditions would be underestimated by a factor of 1.5 to 2.5. Due to the competitive sorption effects between CH₄ and CO₂, the Langmuir equilibrium constants for gas mixtures are influenced by compositional changes, leading to dynamic deviations from those observed under pure gas conditions. This finding contrasts with the traditional extended Langmuir model, which presumes that the equilibrium constants remain unchanged regardless of gas composition. In addition, the displacement study underscores the efficacy of CO2 in displacing CH4, with higher CO2 ratios intensifying displacement effects. The study highlights the substantial impact of real multicomponent scenarios on coal selectivity for CO₂ and CH₄, offering deeper insights into predicting competitive sorption behavior between CO₂ and CH₄ during CO₂-enhanced coalbed methane recovery and carbon storage processes.