Lithofacies and micropore characteristics of shale reservoir directly affect the exploration and development of natural gas. To determine the development potential of shales of the Longmaxi Formation in the Western Hunan‐Hubei Region, the lithofacies types and micropore structure characteristics of the Longmaxi Formation shales have been systematically studied in this paper, based on ordinary thin sections, argon ion polishing–scanning electron microscopy, physical property testing, x‐ray diffraction whole‐rock and clay mineral analysis, isothermal nitrogen, and carbon dioxide adsorptions. According to the principle of ‘laminar structure + total organic carbon (TOC) + mineral composition of felsic, clay, and carbonate minerals’, eight types of shale lithofacies were identified. The effective porosity of the Longmaxi shale ranges from 1.8% to 14.4%, with a peak range from 3% to 6%, while the permeability ranges from 0.001 to 1.27 mD, with an average of 0.106 mD. Combined with the isothermal adsorption experiments, the proportion of mesopores is the largest in the Longmaxi shale, followed by macropores and micropores. Moreover, the pore diameters of mesopores are concentrated between 3 and 10 nm, while those of micropores are concentrated between 0.4 and 0.9 nm. The pore volume of shale is most developed when the content of brittle felsic minerals is 50% ~ 75% and the content of clay minerals is 25% ~ 50%, and the TOC content is positively correlated with the pore volume and specific surface area. There are significant differences in the pore development characteristics of different lithofacies. The shale reservoir space analysis indicates that micropores are controlled by TOC content and clay minerals, while the macropores are controlled by depositional intergranular pores, TOC content, and felsic content, as well as diagenetic pyrite mould pores, microfractures pores, and intercrystalline pores. On the other hand, mesopores are related to a mix of depositional and diagenetic factors with dominant contribution of intergranular pores, intercrystalline pores, organic pores, and intergranular shrinkage fractures pores. It is found that the pore development of massive organic‐rich siliceous shale lithofacies has the best reservoir quality, including well‐connected intergranular pores, intercrystalline pores, organic pores, and shrinkage fractures. Therefore, the massive organic‐rich siliceous shale lithofacies is the dominant fine‐grained reservoir lithofacies in the studied area. Based on understating the pore characteristics of different lithofacies, this study can provide a scientific basis for the prediction of favourable sweet spots of shale gas reservoir in the Longmaxi Formation, western Hunan‐Hubei Region.