The effects of supercritical CO2 (scCO(2)) on coal pores play a critical role in CO2 geological storage-enhanced coalbed methane recovery (CO2-ECBM). To investigate the effects of scCO(2) on the pore structure and connectivity in coals of different ranks, CO2 sequestration processes were replicated using a scCO(2) geochemical reactor. Four coal samples with different ranks were exposed to scCO(2) and water for 240 h under 80 degrees C and 20 MPa. Mercury intrusion porosimetry, nitrogen adsorption tests, and scanning electron microscopy analysis were used to identify the pore volume, pore size distribution, pore connectivity, and pore morphology of the coal samples before and after scCO(2)-H2O treatment. The increase in the macropore volume caused by the scCO(2) is mainly controlled by the pores > 30 mu m, resulted from the dissolution of carbonate minerals with large grain size in organic matter. The coal rank has a positive influence on the volume and specific surface area of the pores > 30 mu m, whereas coal rank is more significant for macropore specific surface area in the high-volatile bituminous coal and macropore volume in the low-volatile bituminous, semi-anthracite, and anthracite coal. With an increase in the coal rank, the volume and specific surface area of the mesopores increase. The changes in the mesopore volume in the high- volatile bituminous coal are caused by changes in the pores 20-50 nm in diameter, while these changes in the low-volatile bituminous coal, semi-anthracite, and anthracite are caused by changes in the pores < 20 nm, due to the formation of dissolution- created pores in minerals; additionally, many pores < 3 nm are generated by the scCO(2). At the macropore scale, the scCO(2) increases the volume of the non-effectively interconnected pores more than that of the effectively interconnected pores, indicating that the scCO(2) has a weak effect on the increase in macropore connectivity. The volume of the effectively interconnected pores increases more at the mesopore scale than at the macropore scale, and the scCO(2) treatment increases the connectivity of the mesopores.