To elucidate the reservoir characteristics of organic-rich siliceous shale of the Upper Permian Dalong Formation in western Hubei, this study focused on the drilling cores of Well ED-2. Various techniques, including a mineral composition analysis, an organic carbon content analysis, a vitrinite reflectance measurement, a total porosity determination, field emission scanning electron microscopy (FE-SEM), and low-pressure CO2 and N2 physical adsorption tests, were employed to analyze the mineralogy, organic geochemistry, total porosity, and pore structure characteristics. Additionally, the factors influencing the reservoir performance of the Dalong Formation shale were investigated. The results indicated that the Dalong Formation’s shale was characterized as an organic-rich siliceous shale. Organic matter was mainly of sapropelic type, with a relatively high thermal evolution degree and Ro ranging from 2.59% to 2.76%. The total porosity of the Dalong Formation’s siliceous shale was low, indicating poor reservoir properties. Organic matter pores were highly developed, mainly the ones formed after the hydrocarbon generation of solid asphalt. Micropores and mesopores were the dominant pore types in the shale, with macropores being significantly less abundant. The study further revealed that the pore volume and specific surface area exhibited a significantly positive correlation with total organic carbon (TOC) content and clay minerals, while demonstrating a weak negative correlation with quartz content. The comprehensive analysis revealed that there were two factors contributing to the poor physical properties of organic-rich siliceous shale in the Dalong Formation. Firstly, in siliceous shale with a high quartz content, the siliceous component was partly derived from the siliceous cementation of hydrothermal fluids. This process led to the formation of secondary quartz that filled intergranular pores, resulting in a decrease in macropore volume, total porosity, and a weak negative correlation with quartz content. Secondly, in siliceous shale with a relatively high clay mineral content, the organic matter was subjected to stronger compaction due to the relatively low content of brittle minerals. This compaction caused the destruction of most macropores, leaving behind primarily micropores and mesopores. Consequently, the average pore size decreased, leading to poor physical properties.