The methods of nuclear magnetic resonance (NMR) spectroscopy, mercury injection porosimetry (MIP), and gas-water relative permeability (GWRP) were used to reveal the pore structure and permeability characteristics of high-rank coal reservoirs in the Bide-Santang basin, western Guizhou, South China, to provide guidance for coalbed methane (CBM) exploration and exploitation and obtain direct insights for the development of CBM wells. The results indicate that the coal reservoirs in the study area are characterized by well-developed adsorption pores and poorly developed seepage pores. The bimodal NMR transverse relaxation time (T2) spectra and the mutation in the fractal characteristic of the MIP pore volume indicate poor connectivity between the adsorption pores and the seepage pores. As a result, the effective porosity is relatively low, with an average of 1.70%. The irreducible water saturation of the coal reservoir is relatively high, with an average of 66%, leading to a low gas relative permeability under irreducible water saturation. This is the main reason for the low recovery of high-rank CBM reservoirs, and effective enhanced CBM recovery technology urgently is needed. As a nondestructive and less time-consuming technique, the NMR is a promising method to quantitatively characterize the pores and fractures of coals.