The hydrogeological conditions of Huainan Coalfield are complex. The Taiyuan formation limestone water (Taihui water) in this area is a direct threat to the water source of the 1# coal mining floor. In order to prevent and control water disasters, Gubei Coal Mine adopted ground high-pressure grouting with fly ash cement to block the hydraulic connection between the Taiyuan formation limestone aquifer and the Ordovician limestone aquifer. However, the injected slurry will destroy the original hydrochemical balance of Taihui water and change its hydrochemical characteristics. Taking the influence area of the 2# karst collapse column in the Beiyi 1# coal mining area of Gubei Coal Mine as an example, a total of 25 Taihui water samples were collected. The hydrochemical characteristics and evolution law of Taihui water before and after grouting are studied via the multivariate statistical method. The research methods include constant index statistics, Piper diagram, correlation analysis, ion combination ratio, and saturation index analysis. The results show that after grouting, the concentrations of Na+ + K+, Ca2+, Mg2+, and Cl− in Taihui water decrease, while the concentrations of SO42− and HCO3− increase. The average values of PH and TDS become larger. The hydrochemical types of Taihui water are more concentrated, mainly HCO3-Na and Cl-Na. The correlations between conventional indicators decrease. According to the analysis of ion combination ratio, dissolution, cation exchange, and pyrite oxidation mainly occur in Taihui water, and these effects are enhanced after grouting. The saturation index results show that after grouting, the saturation index of dolomite, calcite, and gypsum is significantly reduced, and the saturation index of rock salt is slightly increased. The conclusion of this study is that the hydrochemical characteristics of Taihui water are greatly affected by fly ash cement. Moreover, because fly ash cement contains a lower calcium oxide content than ordinary Portland cement, the effect of fly ash cement on the ion concentration of Taihui water and the resulting hydrogeochemical effect are significantly different. Therefore, in the treatment of mine water disasters, the hydrogeochemical evolution law affected by fly ash cement grouting should be identified.