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Heterogeneous nanopore structure and distribution regulate the gas trapping, desorption kinetics, and diffusion in shale matrices. In shale, pores range from continuous micro- and mesopore size distributions, varying with organic (total organic matter-TOC) and inorganic constituents (clay content, Fe-bearing minerals, quartz, etc.). Previous research only showed a linear relationship of pore parameters with these intrinsic properties of shale, which limits our understanding of the concurrent influence of multiple intrinsic rock properties. As a result, in this work, we established multivariate dependency of nanopore structure, distribution, and complexity (from low-pressure N2 and CO2 sorption and small-angle scattering; SAXS/MSANS) in the previously little-studied Cambay shales and provided a better tool (partial least square regression) for analyzing the simultaneous effect of intrinsic shale properties on multiply connected pore-parameters. Furthermore, we discretized continuous pore-size distribution into individual pore families using deconvolution to understand the pore space better. Additionally, predicted shale formation environment in terms of deposition probability (P+) and dissolution probability (P−) using a dynamic model of the fractal interface by precipitation and dissolution. Our findings indicate that the Cambay shales have a high potential for future hydrocarbon exploration (S2: 2.42–12.04 mg HC/g rock), “very good” (2-4 wt.%) to “excellent” (>4 wt.%) TOC content, and thermally mature type II–III admixed and type III kerogen. Deconvolution of the micro- and mesopore size distributions reveals that pore width (w) ranges ∼15.30–35 nm occupies greater than 50% of the total pore volume, and its pore volume increases with the presence of quartz, Fe-bearing minerals, and clay content. However, pores with w∼ 3.60–15.30 nm increase exclusively with TOC. In the micro- and early mesopore region, pore volume decreases with TOC from w∼ 0.30–0.75 nm and increases with TOC from w∼ 0.75–3.60 nm. Furthermore, TOC in shale increases the specific surface area and pore volume (micro-, meso-, and total pores), enhancing both sorption and free gas storage capacities. Cambay shales were likely deposited in three distinct environments, with precipitation probability (P+) values of 1, 0.7–0.8, and 0.5, as revealed by a fractal dimension (Ds) analysis of multiple samples.