Groundwater is the most important source of drinking water. Fluoride was found in high concentrations in the groundwater from deep wells of the water supply in the southern main Ethiopian rift. The high concentration of fluoride is dominantly geogenic rather than anthropogenic in origin, as the agricultural area was not found to be contaminated with NO 3 − . Knowledge of fluoride enrichment will help to provide management plans for developing deep groundwater and minimizing the health risks of exposure to fluoride. The chemical processes of fluoride were investigated in the waters in the Bilate River basin using hydrochemical and isotopic tools. The F − concentration ranged from 0.5 to 1.29 mg/L in water from shallow wells and from 0.48 to 5.61 mg/L in water from deep wells. Seventy percent of deep well samples had F − > 1.5 mg/L higher than the World Health Organization potable guideline. The high fluoride concentration in the groundwater was mainly situated in the rift valley of the Bilate River basin, in contrast with low F − groundwater in the highland. The concentration of fluoride was lowest in Ca-Mg-HCO 3 type groundwater and highest in Na-HCO 3 type groundwater. Moreover, F − was positively correlated with HCO 3 − , Na + , Na + /Ca 2+ and pH in groundwater and Na + /Ca 2+ ratios were increased along the flow path. Hydrogeological, hydrodynamic and hydrochemical conditions are responsible for fluoride accumulation in the deep aquifers. Strong dynamic flow in highland areas flush away weathered chemical components (e.g., F − ). Thus, surficial weathering is not a major controlling factor for high concentrations of Fluoride in deep groundwater but the combination of silicate hydrolysis and ion exchange mainly control fluoride enrichment in stagnant flow environments.In past decades, researchers have studied the geographical distribution of fluoride concentration [6-8] and its relationship with dental caries, dental fluorosis and skeletal fluorosis [9][10][11] in the Ethiopian rift valley. Water quality and fluoride sources were investigated in the central Ethiopian rift [12]. The occurrence of health problems related to fluoride are well documented in the Central Ethiopian rift valley, whereas hydrogeochemistry and F − enrichment mechanism in the southern Ethiopian rift valley have not yet been investigated and are poorly understood.Fluoride in groundwater is related to various rock types, that is, sedimentary rocks [13,14], igneous rock [12,15], or metamorphic rock [16,17], influenced by geochemical and climatological conditions [18]. Volcanic emissions and geothermal water are also sources of fluoride in groundwater [19][20][21]. Fluorine-bearing minerals like topaz, fluorite, tourmaline, muscovite, biotite, hornblende and villianmite, release F − through weathering and water-rock interaction [22][23][24]. Besides natural sources, fluoride can be derived from anthropogenic activity including mining activities, industrial emissions and agricultural fertilizers [25][26][27].The south Ethiopian rift is locate...