To study the influence of water–rock interactions on the deterioration of rock, particularly the problems of the complex dissolution mechanism of dolomite and the difficulty in establishing chemical damage, dolomite obtained from a tunnel in Yuxi City was utilized. The macroscopic and microscopic dissolution characteristics of dolomite were analyzed using an indoor dissolution test combined with the hydrochemical characteristics of the study area, which were found to be favorable for dissolution. The dissolution of dolomite indicates the chemical decomposition of dolomite crystals, and the crystal failure mode is divided into intergranular dissolved pores and intracrystalline micropore development. Under various pH conditions, as H + is immersed in the rock sample, the failure mode of the rock sample develops from longitudinal cracks to transverse and longitudinal staggered cracks. Based on the aforementioned conclusions, in addition to the principle of chemical kinetics and the generalized Lemaitre strain equivalence principle, a damage model suitable for dolomite chemical erosion was defined. The fitting degree between the calculated value of uniaxial compressive strength and the experimental value reaches 98%, which is of excellent prediction accuracy and reliability. The model for dolomite chemical damage proposed herein provides a theoretical basis for dolomite dissolution damage; the theory of rock chemical damage is thereby enhanced.