Understanding hydrochemical evolution and apportioning pollution sources are prerequisites for effective groundwater protection at the regional scale; nevertheless, the governing processes and anthropogenic drivers in arid regions remain poorly constrained. Here, we present a comprehensive geochemical survey of the Datong River Basin, a representative arid catchment in north-western China. Thirty-seven groundwater samples were analyzed with hydrochemical methods and Positive-Matrix Factorization (PMF) to delineate natural controls and contaminant sources. Results showed that the aquifer is dominated by HCO3-Ca(Mg) water controlled predominantly by silicate and carbonate weathering, modified locally by evapo-concentration and human activities. Water-quality indices classify 70.3% of the samples as excellent, but spatially restricted degradation is evident. PMF resolved three independent sources: a natural end-member enriched in Mn, Na+ and Cl-; a mixed source reflecting domestic wastewater, agricultural fertilizers and rock weathering; and an industrial source dominated by Fe. The mixed source contributes most major ions and chemical oxygen demand (COD), whereas the industrial source accounts for 75.7% of total Fe. These findings provide a robust scientific basis for groundwater management and pollution mitigation in arid regions under similar hydrogeological settings.