The petrophysical properties of rocks have an important influence on shale quality. To characterize the difference of petrophysical properties between organic-rich and organic-poor shale reservoirs, we used the low-field nuclear magnetic resonance (NMR) technique and field emission scanning electron microscopy analysis after argon-ion polishing or natural section to measure porosity and permeability from six core samples from well SY6 in the Sangzhi block, Northwest Hunan province. Some information about pore types, pore structure, residual porosity, movable porosity, and permeability based on the T2 spectrums’ difference of organic-rich and organic-poor shale samples were discussed. The shale sample test results show that the main pores size is mesopore, which provide most of shale gas reservoir space. The continuous peaks demonstrated the pores’ connectivity better than the isolated peaks, and shale gas can migrate freely between these connected pores and fractures. The permeability of all samples calculated by the classic Coates model is extremely low, which is not conducive to the migration of shale gas. We evaluated the dominating factors of NMR porosity and permeability and found that the relationships between NMR porosity and permeability and total organic carbon content, quartz minerals, and clay minerals are not clear, which may be a comprehensive influence. The research results have important guiding significance for shale reservoir quality evaluation in this area.