This study incorporated hydrogeochemical facies, the entropy-weighted water quality index (EWQI), multivariate statistics, and probabilistic human exposure assessment to investigate hydrogeochemistry, analyze groundwater quality, and estimate potential risks to human health in a lithium-rich ore area (Jadar River basin, Serbia). The findings designated the Ca·Mg-HCO3 hydrogeochemical type as the predominant type of groundwater, in which rock weathering and evaporation control the major ion chemistry. Due to the weathering of a lithium-rich mineral (Jadarite), the lithium content in the groundwater was very high, up to 567mg/L, with a median value of 4.3mg/L. According to the calculated EWQI, 86.4% of the samples belong to poor and extremely poor quality water for drinking. Geospatial mapping of the studied area uncovered several hotspots of severely contaminated groundwater. The risk assessment results show that groundwater contaminants pose significant non-carcinogenic and carcinogenic human health risks to residents, with most samples exceeding the allowable limits for the hazard index (HI) and the incremental lifetime cancer risk (ILCR). The ingestion exposure pathway has been identified as a critical contaminant route. Monte Carlo risk simulation made apparent that the likelihood of developing cancerous diseases is very high for both age groups. Sensitivity analysis highlighted ingestion rate and human body weight as the two most influential exposure factors on the variability of health risk assessment outcomes.