Traditional correlation analyses based on whole-rock data have limitations in discerning pore development determinants in shale oil reservoir, given the complex lithology of shale formations and intricate interdependencies (multicollinearity) among geological variables. In this study, mercury injection capillary pressure and digital analysis of scanning electron microscopy were employed to examine the macropore structures of both whole rocks and their constituent lithologies for the Upper Triassic Chang-7 shale of the Ordos Basin. Variations were observed among clay shale (shale primarily consisting of clay-sized mineral grains), massive siltstone and silty laminae within the Chang-7 shale. Through the combination of correlation analysis and scanning electron microscope digital technique, it was demonstrated that total organic carbon content primarily controls the level of macropore development, while lithology primarily governs macropore types and structures. Although quartz and pyrite exhibit correlations with macropore volume, they do not emerge as primary factors; instead, they appear interconnected to total organic carbon. Due to detrital mineral framework preservation during compaction, larger macropores are more developed in massive siltstones and silty laminae than in clay shale. Additionally, silty laminae, situated closer to the source rock and influenced by organic acids, exhibit a higher abundance of larger dissolution pores, potentially favoring shale oil development. This study overcomes traditional method constraints, disentangling multi-correlations, and providing new insights into shale macropore development mechanisms, potentially advancing shale oil exploration and production.