Abstract: The Lower Cambrian shale gas in the western Hubei area, South China has a great resource prospect, but the gas-in-place (GIP) content in different sedimentary facies varies widely, and the relevant mechanism has been not well understood. In the present study, two sets of the Lower Cambrian shale samples from the Wells YD4 and YD5 in the western Hubei area, representing the deep-water shelf facies and shallow-water platform facies, respectively, were investigated on the differences of pore types, pore structure and methane adsorption capacity between them, and the main controlling factor and mechanism of their methane adsorption capacities and GIP contents were discussed. The results show that the organic matter (OM) pores in the YD4 shale samples are dominant, while the inorganic mineral (IM) pores in the YD5 shale samples are primary, with underdeveloped OM pores. The pore specific surface area (SSA) and pore volume (PV) of the YD4 shale samples are mainly from micropores and mesopores, respectively, while those of the YD5 shale samples are mainly from micropores and macropores, respectively. The methane adsorption capacity of the YD4 shale samples is significantly higher than that of the YD5 shale samples, with a maximum absolute adsorption capacity of 3.13 cm3/g and 1.31 cm3/g in average, respectively. Compared with the shallow-water platform shale, the deep-water shelf shale has a higher TOC content, a better kerogen type and more developed OM pores, which is the main mechanism for its higher adsorption capacity. The GIP content models based on two samples with a similar TOC content selected respectively from the Wells YD4 and YD5 further indicate that the GIP content of the deep-water shelf shale is mainly 3−4 m3/t within a depth range of 1000–4000 m, with shale gas exploration and development potential, while the shallow-water platform shale has normally a GIP content of <1 m3/t, with little shale gas potential. Considering the geological and geochemical conditions of shale gas formation and preservation, the deep-water shelf facies is the most favorable target for the Lower Cambrian shale gas exploration and development in the western Hubei area, South China.