Existing methods for shale reservoir stimulation (e.g., hydraulic fracturing) focus mainly on improving the physical recovery of free phase gases from shales. Few studies explore the enhanced recovery of adsorbed methane from shale due to the difficulty in simultaneously separating the recovery of both the adsorbed and free phase gas. In this study, we use an NMR-based methodology to separately evaluate the change in adsorbed and non-adsorbed (free-phase) methane during the injection of CO2. We evaluate mechanisms contributing to the enhanced recovery of adsorbed-gas with CO2 injection (Longmaxi shale, Jiaoshiba field, SW China). Results show that the injection of CO2 can improve the efficiency of recovery of residual gas in the adsorbed phase by an additional 25% and can enhance the percent recovery per hour of adsorbed methane by 11% at ambient pressure and 4% at abandonment pressure. The experiments also demonstrate that a higher concentration ratio of CO2/CH4 is more suitable for CO2-CH4 displacement, and the CO2-CH4 displacement rate is relatively rapid during the early phase of interaction, immediately after injection. Despite inherent uncertainty, these experiments demonstrate the capability of enhancing adsorbed-gas recovery by injection of CO2 into shale.