Based on scanning electron microscopy and nitrogen adsorption experiment at low temperature, the pore types and structures of the Longmaxi Formation shale in the Dianqianbei area, SW China were analyzed, and a molecular model was built. According to mathematical statistics, the validation of the model was solved by converting it into a mathematical formula. It is found by SEM that the pores in clay mineral layers and organic pores occupy most of the pores in shale; the nitrogen adsorption experiment at low temperature reveals that groove pores formed by flaky particles and micro-pores are the main types of pores, and the results of the two are in good agreement. A molecular model was established by illite and graphene molecular structures. Moreover, based on the fractal theory and the Frenkel-Halsey-Hill formula, a modified Frenkel-Halsey-Hill formula was proposed. The reliability of the molecular model was verified to some extent by obtaining parameters such as the fractal dimension, replacement rate and fractal coefficients of correction, and mathematical calculation. This study provides the theoretical basis for quantitative study of shale reservoirs.