In this study, the adsorption and competitive diffusion of methane (CH4) and carbon dioxide (CO2) mixtures through a molecular model of mature type-2 kerogen was investigated using molecular dynamics simulations. The Dual Control Volume-Grand Canonical Molecular Dynamics method was used to analyze the system and the results were focused on the selectivity of kerogen towards mixtures under a wide range of thermodynamic conditions. The results showed that the adsorption selectivity of CO2/CH4 was around 2–4 and decreased with temperature in the range 350–450 K. The Extended Langmuir (EL) model was found to underestimate the selectivity, and a correction was proposed in the form of the Corrected Extended Langmuir (CEL) model, which improved the estimations of the adsorption of CH4/CO2 mixtures in kerogen with only one adjustable parameter independent of thermodynamic conditions. Interestingly, we noticed that, out of equilibrium, the adsorption selectivity was not affected by the flow conditions when a pressure gradient was imposed, and the CEL model can thus be used to describe the contribution of adsorption to the selectivity under flow conditions. The results showed that the ratio of the collective diffusion coefficients of CH4 and CO2 was around 0.3−0.4, which was about two times lower than other simulations found in the literature. To describe the global selectivity, a simple approach combining the CEL model and the average ratio of diffusion coefficients was proposed, resulting in a selectivity of around 1.