This study analyzes samples from the Lower Cambrian Niutitang Formation in northern Guizhou Province to enable a better understanding of total organic carbon (TOC) enrichment and its impact on the pore characteristics of over-mature marine shale. Organic geochemical analysis, X-ray diffraction, scanning electron microscopy, helium porosity, and low-temperature nitrogen adsorption experiments were conducted on shale samples. Their original TOC (TOCo) content and organic porosity were estimated by theoretical calculation, and fractal dimension D was computed with the fractal Frenkel–Halsey–Hill model. The results were then used to consider which factors control TOC enrichment and pore characteristics. The samples are shown to be dominated by type-I kerogen with a TOC content of 0.29-9.36% and an equivalent vitrinite reflectance value of 1.72-2.72%. The TOCo content varies between 0.64% and 18.17%, and the overall recovery coefficient for the Niutitang Formation was 2.16. Total porosity of the samples ranged between 0.36% and 6.93%. TOC content directly controls porosity when TOC content lies in the range 1.0% to 6.0%. For samples with TOC < 1.0% and TOC > 6.0%, inorganic pores are the main contributors to porosity. Additionally, pore structure parameters show no obvious trends with TOC, quartz, and clay mineral content. The fractal dimension D1 is between 2.619 and 2.716, and D2 is between 2.680 and 2.854, illustrating significant pore surface roughness and structural heterogeneity. No single constituent had a dominant effect on the fractal characteristics.