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Water–rock interaction is a common phenomenon in rock mass engineering. Water–rock interaction alters the mineralogical and microstructural properties of a rock mass and leads to engineering problems such as leakage, deformation, and failure of a rock mass. To investigate the local leakage in the limestone reservoir, limestone specimens were taken from the underground chamber. In this study, two test conditions were designed: with and without regular replacement of the reservoir water condition. The results indicated that the porosity increased sharply in the early stages of the soaking. But, the rate of increment dropped after 120 d (regular replacement of reservoir water condition) and 90 d (unchanged reservoir water condition), respectively. The pore in the rock was 4.50 mm deep, while the reservoir water was replaced regularly, which is 1.54 times that of the unchanged reservoir water condition (i.e., 2.50 mm), in 360 soaking days. Relatively, the renewal of reservoir water enhanced the chemical reaction. The water–rock interaction altered the mineralogical composition, spatial structure of the crystal, and pore structure of the rock. The change in the longitudinal wave velocity Vm measures the state of pore development. The porosity evolution model for limestone rock was established by considering the impact of dissolution on the spatial structure of the crystal skeleton. The model accurately predicted the variation trend of porosity in the limestone rock under water–rock interaction. [ABSTRACT FROM AUTHOR]