The low gas permeability of coal formations with limited coal pores and fractures leads to difficulty in coalbed methane exploration. High-voltage electrical pulse has a potential application in enhanced coalbed methane recovery. In this study, we discuss the microscopic characteristics of anthracite coals treated by high-voltage electrical pulse. We find that C, O, and other coal elements constituting oxygenic groups, which mainly account for gas adsorption, decreased slightly after high-voltage electrical pulse treatment, indicating that elemental variation may have little influence on gas adsorption. The scanning electron microscopy and low-pressure nitrogen gas adsorption (LP-N2GA) results show that the cumulative micropore volumes of high-voltage electrical pulse-treated coals were much larger than those of original coals. The mercury intrusion porosimetry results show that the cumulative macropore volumes, which act as gas migration channels in coal increased. Additionally, high-voltage electrical pulse-treated coals were found to have smaller entrapment areas, indicating that gas migration was enhanced.