The migration phenomenon of deep shale gas is a subject that has yet to be fully comprehended, specifically regarding the migration ability of deep shale gas. This study focuses on the Longmaxi Formation in the southern Sichuan Basin, utilizing it as an example. Various experimental techniques, such as temperature-driven nitrogen and carbon dioxide adsorption, high-pressure mercury intrusion, XRD, and TOC analysis, are employed. The goal is to analyze the pore structure and fractal characteristics of the Longmaxi Formation shale. Additionally, the study aims to calculate its Knudsen number based on parameters like temperature gradient and pressure coefficient. The migration ability of the Longmaxi Formation shale in southern Sichuan Basin is also discussed. The results show the following: (1) The pore volume distribution of the Longmaxi Formation shale in the study area ranges from 0.0131 to 0.0364 cm3/g. Mesopores contribute approximately 56% of the pore volume, followed by micropores with a contribution rate of about 26%, and macropores contributing approximately 18%. Additionally, the Longmaxi Formation shale exhibits strong heterogeneity, with the fractal dimension (D1) of mesopores ranging from 2.452 to 2.8548, with an average of 2.6833, and the fractal dimension (D2) of macropores ranging from 2.9626 to 2.9786, averaging 2.9707. (2) The fractal dimensions of shale were significantly influenced by organic matter, inorganic minerals, and pore structure parameters. D1 and D2 were positively correlated with TOC, clay mineral content, and specific surface area, while exhibiting negative correlation with quartz. However, the correlations with calcite content, pore volume, and average pore size were not significant. (3) The proportion of pores satisfying Darcy flow in the Longmaxi Formation shale was approximately 3.7%–11.8%, with an average of 6.6%. Consequently, the migration capability of shale gas can be calculated using Darcy’s law. Furthermore, the migration capability of shale gas is controlled by D2, specifically the surface area, and the connectivity of macropores.