Characteristics of shale pore structures may play an important role in natural gas accumulation and consequently estimating the original gas in place. To determine the pore structure characteristics of Niutitang marine shale in the Sangzhi block, we carried out adsorption-desorption (LP-GA), adsorption (LP-GA), and methane isothermal adsorption on shale samples to reveal the pore size distribution (PSD) and its impact on the adsorption capacity. Results indicate that the Niutitang Shale is in stages of maturity and overmaturity with good organic matter, and they also indicate well-developed interparticle, intraparticle, and organic pores. Quartz and clay are found to be the main minerals, and the high illite content means that the Niutitang Shale is experiencing the later stage of clay mineral transformation. Various-sized shale pores are well-developed, and most of them are narrow and slit-like. For pores with diameters of 2–300 nm measured with LP-GA, mesopores (2–50 nm) contribute most of the total specific surface area (SSA) and total pore volume (TPV) in comparison to macropores (50–300 nm). For micropores () tested by LP-GA, the PSD appears to be multimodal; shale pores of 0.50–0.90 nm diameter contribute most of the SSA and TPV. -SSA and -SSA indicate positive correlations with their corresponding TPV. The total organic matter (TOC) has good correlation with the SSA and TPV of micropores. The Langmuir volume positively correlates with the total SSA. Additionally, the TOC content has a good correlation with the Langmuir volume, which is consistent with the observation of well-developed fossils of diatoms and organic pores. As an important source of organic matter, more diatoms mean more organic matter, larger TOC values and quartz content, larger SSA and TPV of micropores, and, of course, stronger shale adsorption capacity. The results provide important guidance for the exploration and development of shale gas existing in the Sangzhi block.