The adsorption capacity of coal with respect to carbon dioxide (CO2) is greater than that of methane (CH4). Studying the CO(2 )replacement of CH4 in coal is essential to understanding the mechanism behind CO2-enhanced coalbed methane. In this paper, scanning electron microscopy was used to qualitatively study the influence of CO2 injection pressure on the fracture characteristics of coal. The time effect of the CH4/CO2 adsorption and the effect of the CO2 injection on the CH4 adsorption were quantitatively studied using low-field nuclear magnetic resonance. The results suggest three different CH4 states in the coal samples: CH4 adsorbed on the pore surface, free CH4 in the pore center, and free CH(4 )between the coal particles. Indeed, the greater the CO2 injection pressure, the more developed the fracturing and network, which, in turn, increases connectivity. As the adsorption time of CH4/CO(2 )increases, the adsorption rate of CO2/CH4 gradually decreases. In essence, CO(2 )preferentially replaces the CH4 of the minipores. As the CO2 injection pressure increases, the difference between the CO2 equilibrium pressure and the initial injection pressure increases. Moreover, the CH4 production rate increases, the transverse relaxation time (T-2) spectrum of the adsorption-state area decreases, the T-2 spectrum of the free-state area increases, and the number of adsorption holes gradually decreases, whereas the number of seepage holes increases.