Thermal maturity of the shales from the Ziliujing Formation of the Jurassic age in the Sichuan Basin is in the hydrocarbon generation window, which makes it a candidate for shale oil and gas development. The meso- and macropore characteristics and heterogeneity of shales are important factors affecting the occurrence and development of oil and gas. However, the meso- and macropores of the Ziliujing shales have not been systematically studied. Thus, the mineral compositions and total organic carbon (TOC) of samples from this formation, as well as its pore structure, are analyzed by low-temperature N2 adsorption technique. Moreover, the heterogeneity of the pores was determined by multifractal analysis. The results show that the Ziliujing shales can be classified into three types according to the distributions of mineral compositions of carbonate and mixed and argillaceous shales. Results revealed that the smallest meso- and macropore volume (PV), the smallest specific surface area (SSA), and the largest average pore diameter (APD) occur in the carbonate shales. However, the largest PV and SSA and the smallest APD are observed in the argillaceous shales. The porosity of carbonate shales is mainly concentrated between 5 nm and 30 nm. Compared with carbonate shales, the porosity with pore sizes less than 30 nm of mixed and argillaceous shales shows a rapid increase. Furthermore, inorganic minerals are the main factors affecting the pore distributions, while TOC shows a weak effect. Herein, clay minerals significantly increase the mesopore volume and the pore number with a size of less than 30 nm. The Dq-q curves reveal that the meso- and macropore distributions of Ziliujing shales show multifractal behavior, but the multifractal characteristics of pores of various shales are distinctly different. The information dimension D1, the Hurst exponent H, and the width of the right side D0–D10 are key indicators to distinguish the local variations within the pore structure of different types of shales. The carbonate shales have the largest multifractal spectra width and the smallest D1 and H, while the opposite trend is found for the argillaceous shales. Clay minerals reduce the heterogeneity of the meso- and macropore distributions and increase the pore connectivity. Nevertheless, the carbonate minerals exhibit a reverse trend. Finally, it was found that TOC does not impact pore complexity as much. Collectively, this study supports our understanding of the occurrence of shale oil within various reservoir facies, thereby providing a guideline for future explorations in the Ziliujing Formation of the Jurassic age in the Sichuan Basin.