Hydrochemical analysis, geological study and evaluation of hydrogeochemical processes play a crucial role to understand the variability of fluoride ion concentration in groundwater. The present study is focused on a watershed boundary comprising of parts of two river basins namely Ruparail and Banganga within Bharatpur district of Rajasthan in India. Administratively, the study area is covered in five blocks of Bharatpur district viz. Deeg, Kaman, Nagar, Pahari and Kumher. The study area and sampling locations were identified based on the spectral signatures of satellite data, literature study and field-based experience. Seventy-five groundwater samples were collected for pre and post-monsoon seasons, separately. The hydrochemical results have shown that Banganga basin has experienced greater fluoride enrichment in groundwater as compared to Ruparail basin. Both the basins have experienced more groundwater samples in the class of high-risk water (more than 1.5 mg/l F-) during the post-monsoon season due to mineral dissolution with the surface run-off water in the aquifer material. The shallow aquifers (< 40 m bgl) have experienced high fluoride distribution in groundwater as compared to deeper aquifers (> 40 m bgl). The spatiotemporal interpolation maps for fluoride ion concentration generated by following inverse distance weighted (IDW) method have shown the varied fluoride concentration with geologic, geomorphic and seismo-tectonic features. Chadha's plot for hydrochemical facies has revealed that the groundwater of the study area is mainly of Na-Cl and Ca-Mg-Cl type. The evaluation of hydrochemical facies has suggested that Na-Cl water type is having elevated fluoride ion concentration as compared to Ca-Mg-Cl and Ca-Mg-HCO3 water types. The interpretation of hydrogeochemical processes based on scatter plots of hydrochemical parameters has revealed that processes such as silicate weathering, direct-ion exchange, mineral dissolution and rock-water interaction are responsible for fluoride augmentation in groundwater. The enrichment is also governed by evaporation, semiarid environment, salinity hazard and overdraft of groundwater. The water types having inhibited fluoride ion concentration are found dominated with carbonate weathering and recharge water (Ca-Mg-HCO3 type) and reverse-ion exchange process (Ca-Mg-Cl type). Moreover, the geochemical modeling is indicative of under-saturation of fluorite with over-saturation of calcite and dolomite, augmenting fluoride ion concentration in groundwater. The comprehensive understanding of hydrogeochemical processes controlling fluoride enrichment is found useful for planning strategies adopted for providing safe drinking water in a sustainable way.