The increasing salinization of groundwater renders it challenging to maintain the water quality. Moreover, knowledge regarding the characteristics and mechanism of groundwater salinization in mining areas remains limited. This study represents the first attempt of combining the hydrochemical, isotope (δD, δ¹⁸O, δ³⁷Cl, and ⁸⁷Sr/⁸⁶Sr) and multivariate statistical analysis methods to explore the origin, control, and influence of fluoride enrichment in mining cities. The TDS content of groundwater ranged from 275.9 mg/L to 2452.0 mg/L, and 54% of the groundwater samples were classified as class IV water according to China's groundwater quality standards (GB/T 14848–2017), indicating a decline in the water quality of the study area. The results of the groundwater ion ratio and isotope discrimination analysis showed that dissolution and evaporation involving water-rock interactions and halite were the main driving processes for groundwater salinization in the study area. In addition to the hydrogeological and climatic conditions, mine drainage inputs exacerbated the increasing salinity of the groundwater in local areas. The mineral dissolution, cation exchange, and evaporation promoted the F⁻ enrichment, while excessive evaporation and salinity inhibited the F⁻ enrichment. Gangue accumulation and infiltration likely led to considerable F⁻ enrichment in individual groundwater regions. Extensive changes in the groundwater salinity indicated differences in the geochemical processes that controlled the groundwater salinization. Given the particularity of the study area, the enrichment of salinization and fluoride triggered by mining activities cannot be ignored.