The development of coalbed methane not only ensures the supply of natural gas but also reduces the risks of coal mine accidents. The micropore structure of coalbed methane reservoir affects the seepage of coalbed methane; improvement of pore structure is one of the effective methods to enhance the efficiency of coalbed methane exploitation. In this study, low-pressure nitrogen gas adsorption, specific surface area analysis, nuclear magnetic resonance spectroscopy, and centrifugation experiment were used to evaluate the effect of ethanol on coal microscopic pore structure and fluid distribution during hydraulic fracturing. Seven coal samples were collected from the No. 3 coal seam in Zhaozhuang Mine, Qinshui Basin. The samples are mainly composed of micropores, transition pores, and mesopores. The experimental results show that ethanol can significantly change the pore structure by increasing the pore diameter. The average specific surface area, pore volume, and pore diameter of rock samples before ethanol immersion are 1.1270 m2/g, 0.0104 cm3/g, and 14.20 nm, respectively. The three parameters of rock samples after ethanol immersion are 0.5865 m2/g, 0.0025 cm3/g, and 29.37 nm. Ethanol improves the connectivity between micropores and mesopores. The average irreducible fluid saturation of samples saturated with formation water after centrifugation is 86%, and the average irreducible fluid saturation of samples soaked in three concentrations of ethanol solution decreases. It is considered that an ethanol solution of 0.4% concentration has the best effect on improving the pore structure and fluid distribution.