The surface chemistry and pore-fracture morphology of coals are critical to the process of CO, sequestration in coal seams with enhanced coalbed methane (CH4) recovery (CO2-ECBM). To assess the influence of deionized water-CO2 mixture (DH2O-CO2) exposure on these properties, the interaction of DH2O-CO2 with three rank coals, i.e., sub-bituminous coal (SBC), high volatile bituminous coal (HVBC), and anthracite, was conducted on a dynamic supercritical fluid extraction system with a temperature of 45 degrees C and an equilibrium pressure of 12 MPa. Characterization methods including proximate analysis (PA), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), probe molecule (N-2/CO2) adsorption, and low-field nuclear magnetic resonance (NMR) were adopted to fully address the changes in surface functional groups and pore-fracture characteristics. The results indicate that the geochemical interaction occurs between the mineral matters and DH2O-CO, as demonstrated by the change in the content of clays, carbonates, and sulfates in the coal matrix. DH2O-CO2 exposure also causes a decrease in the content of organic oxygen and carbon-oxygen functional groups, especially for COOH groups, but an increase in C-C/C-H species, and the impact is strengthened with the decreasing coal rank. The aforementioned aspects illustrate the reconfiguration of surface geometry and the chemical interaction between DH2O-CO2 and the oxygen-containing functional groups. In combination with the reduced volatile matter and organic sulfur groups, the results imply that the extraction effect and chemical interaction may contribute to the change in coal surface chemistry. DH2O-CO2 interaction degrades the accessibility of micropores of all the coals, whereas the reverse trend is found for macropores and fractures. DH2O-CO2 interaction facilitates the development of macrop ores and fractures and thus improves the permeability of coal seams, which can be attributed to the dissolution and mobilization of mineral matters by the acid water and the shrinkage of coal induced by the water loss. The variation of mesopores due to DH2O-CO2 exposure is strongly related to coal rank and surface chemistry. Specifically, the decreasing mesoporosity is found for SBC, whereas this trend is opposite for HVBC and anthracite. The relationship between adsorption pores (<100 nm) and macropores and fractures of SBC decreases, while the opposite trend is recorded in HVBC and anthracite after fluid exposure. The results obtained from this work indicate that the net effect of the surface chemistry and the accessibility of porosity in various rank coals after fluid exposure is crucial for the potential of CH4 recovery and CO2 storage during the implementation of the CO2-ECBM process.