The characterization of the pore structure and shale gas content provides useful information for shale gas reservoir assessment and evaluation and guides the exploration and development of shale gas. Fresh core samples obtained from three different basin formations in China were analyzed by field-emission scanning electron microscopy, low-pressure CO2 and N-2 gas adsorption-desorption, high-pressure mercury intrusion, and methane adsorption experiments to clarify the pore structure characteristics of coal-bearing shales and their effects on shale gas content. The inter- and intraparticle pores, organic matter pores, and microfractures were well developed in coal-bearing shales. These pores had different geneses, morphologies, and sizes with main diameters of <6.5 and 80-200 nm and the main shape of slit, taper, and ink bottle. Pores with diameters <10 nm dominated the shale pore networks. Shale gas content was directly influenced by shale pores, and small pores had a large surface area, which resulted in the high adsorption capacity of shale gas. Clay mineral and total organic carbon contents positively controlled the pore structures and shale gas adsorption, whereas brittle minerals were counterproductive. Coal bearing shale gas content was lower than marine shale gas content, with an adsorption gas content percentage of 50-85%. The proportion of adsorbed gas decreased with the increase of pore size diameters, whereas the proportion of free gas increased. When the pore size diameter reached approximately 3.5 nm, the free and adsorption gases reached dynamic balance. The adsorption gas content would be slightly low with pore size ranges of >6.5 nm, whereas the free gas content would be stable and merely increase in the range of 100-300 nm.