Methane gas is mainly present in coal in two forms: free and adsorbed. There are a large number of closed pores inside the coal, which makes it difficult to measure the gas content of the coal. Therefore, studying the nanoscale closed pores of coal is of great importance for gas control. To study the pore structure characteristics of coal with different deformation degrees and to analyze the volume fraction of closed pores in coal, various coal samples were analyzed by the low-temperature liquid nitrogen adsorption method (LT-N2GA), the carbon dioxide adsorption method, and small-angle X-ray scattering (SAXS). The variation of parameters such as the pore size, pore volume, specific surface area, and degree of metamorphism was compared by using different methods to obtain the proportion of the closed pore volume of different coal samples. The results show that with the increase of the degree of coal metamorphism, the total pore volume and specific surface area of coal samples show a decreasing trend first and then an increasing trend, while the average pore diameter of coal samples gradually increases first and then decreases sharply. When the degree of deterioration of coal is low (volatile content > 20%), the closed pores of coal account for more than 48% of the open pores. When the degree of deterioration of coal samples is relatively high (volatile content