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In the Luzhou Block of the southern Sichuan Basin, the deep Longmaxi shales have become important exploration targets in recent years. However, the water-bearing properties of these shales are still unclear, which significantly limits evaluations of reservoir pore structures and gas-in-place (GIP) contents. In this study, twelve fresh shale core samples were collected at the well site, and the pore water (CPW) and equilibrium water (CEW) contents, as well as the pore structures of the shales, were analyzed under both as-received and dried conditions. The results indicate that the deep shales have low water-bearing extents with a pore water content (CPW) of 3.82–16.67 mg/g, and that both the organic matter (OM) and inorganic matter (IM) pores can be used for pore water storage. The extent of influence of pore water on nonmicropores and IM pore structures is more significant than that on micropores and OM pore structures. Meanwhile, the pore water obviously reduces the retention effects of nanopores and may block nanopores with pore widths < 0.5 nm. An average of 40% of pore spaces were taken up by pore water in the studied deep shales in the Luzhou Block, and the residual pore surface area and pore volume of the shales were mainly contributed from micropores and nonmicropores, respectively. [ABSTRACT FROM AUTHOR]