Multi-lithological super-imposed coal measure strata offer strong potential for CO2 geo-sequestration while simultaneously enabling significant gas recovery. This study examines multiphase fluid (adsorbed/free CH4 and CO2) transport dynamics and enhanced coal measure gas production concurrent with geological CO2 sequestration. Herein, a reservoir model of stacked coal seam, shale and sandstone strata based on the in-situ geological characteristics of the Longtan Formation of the Songzao Coalfield (Sichuan Basin, China) is developed to evaluate the enhanced gas recovery characteristics. Evaluation of concurrent CO2 geological sequestration and CH4 co-production reveal the initial natural depressurization-driven gas production from the reservoir before CO2 injection subsequently elevates gas pressures. Coupled Thermal-Hydraulic-Mechanic (THM) simulation reveals three key multiphase transport mechanisms: (1) competitive adsorption-driven CH₄ displacement with a 3.2:1 CO₂/CH₄ molar replacement ratio in the coal matrix; and (2) differential phase migration velocities (Vfree_gas > Vadsorbed_gas) resulting in transient saturation inversions. Continuous CO₂ injection at 7 MPa sequestered ~45.4 t CO₂ with 88.61% adsorbed-phase storage, and CH₄ recovery increased to 42.22% (+10.16% vs. natural depletion). A Phase-specific analysis revealed that the sequestered CO2 exhibits distributed differently among coal, shale, and sandstone formations, in the proportions of 43.78%, 55.36%, and 0.86%, respectively. This work provides fundamental insights into multiphase transport and control for optimizing CO2-enhanced recovery in multi-lithological super-imposed coal measure systems.