Properly identifying microscopic pore structure properties of shale reservoirs is essential for developing efficient extraction techniques of shale hydrocarbons. To understand the unique and complex pore network of the Northern Guizhou shale reservoir, shale samples from the Wufeng-longmaxi Formation were investigated using different analytical techniques, X-Ray Diffractometry, low-pressure nitrogen gas adsorption-desorption isotherms, and Mercury intrusion capillary porosimeter. Results indicate that the Wufeng-longmaxi formation is mainly composed of a high quantity of quartz ranging from 0.6 % to 64.1 % and an average extent of 55.825 %, the lowest amount of potassium feldspar ranging from 0.6 % to 2.2 % and an average extent of 1.45 % with Total organic contents ranging from 3.672 to 5.209 %. Similarly, the BJH adsorption techniques for pore volume and area were investigated. The results indicate the dominance of the mesopore with pore size ranging from 2.03 nm to 40nm, average pore volume of 0.073715 m3/g, and average pore area of 13.0324 m2/g. The pore throat distributions from MICP showed drain pressure and median pore throat radius ranging from 0.47 to 13.79 MPa and 0.05–0.08 μm, respectively. Suggested complementary experimental techniques reveal the connectivity of pore networks of the Wufeng-longmaxi Formation shale reservoir, which shows a high production potential of hydrocarbons. The findings of this study can provide a valuable understanding of fluid transport properties and storage space of shale gas that can help decision-makers as they set exploration initiatives for shale gas reservoirs.