Shale samples of Silurian Longmaxi Formation in the Changning area of the Sichuan Basin, SW China, were selected to carry out scanning electron microscopy, CT imaging, high-pressure mercury injection, low-temperature nitrogen adsorption and imbibition experiments to compare the hydration characteristics of montmorillonite and illite, analyze the main factors affecting the water block removal of shale, and reveal the mechanisms of pore structure evolution during shale hydration. The hydration characteristics of shale are closely related to the composition of clay minerals, the shale with high illite content is not susceptible to hydration and thus has limited room for pore structure improvement; the shale with high montmorillonite is susceptible to hydration expansion and thus has higher potential of pore structure improvement by stimulation; the shale with high illite content has stronger imbibition in the initial stage, but insufficient diffusion ability, and thus is likely to have water block; the shale with high montmorillonite content has weaker imbibition in the initial stage but better water diffusion, so water blocking in this kind of shale can be removed to some degree; the shale reservoir has an optimal hydration time, when it is best in physical properties, but hydration time too long would cause damage to the reservoir, and the shale with high illite content has a shorter optimal hydration time; inorganic cations can inhibit the hydration of clay minerals and have stronger inhibition to illite expansion, especially K⁺; for the reservoir with high content of montmorillonite, the cation content of fracturing fluid can be lowered to promote the shale hydration; fracturing fluid with high K⁺ content can be injected into reservoirs with high illite content to suppress hydration.