Shiqian County, located within a key geothermal fluids belt in Guizhou Province, China, has abundant underground hot water resources. Therefore, elucidating the hydrogeochemical characteristics and formation mechanisms of thermal mineral water in this area is essential for evaluating and sustainably utilizing regional geothermal fluids. This study focuses on the Shiqian Hot Spring Group and employs integrated analytical techniques, including rock geochemistry, hydrogeochemistry, isotope hydrology, digital elevation model (DEM) data analysis, remote sensing interpretation, geological surveys, mineral saturation index calculations, and PHREEQC-based inverse hydrogeochemical modeling, to elucidate its hydrogeochemical characteristics and formation mechanisms. The results show that strontium concentrations range from 0.06 to 7.17 mg/L (average 1.65 mg/L) and metasilicic acid concentrations range from 19.46 to 65.51 mg/L (average 33.64 mg/L). Most samples meet the national standards for natural mineral water and are classified as Sr-metasilicic acid type. Isotope analysis indicates that the geothermal water is recharged by meteoric precipitation at elevations between 911 m and 1833 m, mainly from carbonate outcrops and fracture zones on the southwestern slope of Fanjingshan, and discharges south of Shiqian County. The dominant hydrochemical types are HCO₃·SO₄-Ca·Mg and HCO₃-Ca·Mg. Strontium is primarily derived from carbonate rocks and celestite-bearing evaporites, whereas metasilicic acid mainly originates from quartz dissolution along the upstream groundwater flow path. PHREEQC-based inverse modeling indicates that, during localized thermal mineral water runoff in the middle-lower reaches or discharge areas, calcite dissolves while dolomite and quartz tend to precipitate, reflecting calcite dissolution-dominated water–rock interactions and near-saturation conditions for some minerals at late runoff stages.