Statistical analysis was used to study the hydrogeochemical evolution of an Ordovician limestone aquifer group in the Hancheng mining area. Before mining, the groundwater flowed from northwest to southeast, the water type was primarily SO4–HCO3, and was mainly controlled by the tectonic structure and the specific hydrogeological conditions. After 40 years of mining, two large groundwater depression cones had formed, centered on the Sangshuping and Xiangshan coal mines in the north and south zones, respectively. The groundwater dropped by ≈ 20 m in the center of the depression cones due to over-exploration and mine water inrush, which changed the groundwater flow field significantly. Both the total dissolved solids and the concentrations of major ions increased 2.3- to 4.7-fold, and the water type changed to SO4–Cl. The saturation indices (SI) of the minerals along the two simulated paths both increased, indicating that the groundwater would dissolve minerals as it flowed, which verified the groundwater flow field. Groundwater quality deteriorated due to a mixture of old acidic pit water and hypersaline water intruding from the deep district. When studied vertically, the concentrations of major ions and SI of calcite and limestone increased, due to the limited cycling of water from shallow to deep. The coincidental Ca2+ and Mg2+ increases were caused by calcite-replacing dolomitization reactions. To summarize, long-term coal mining adversely affected the area’s groundwater flow field and hydrogeochemical evolution, and effective action should be taken to prevent the Ordovician groundwater from continuing to deteriorate.