Hydrochemical studies were conducted in Chinnaeru river basin of Nalgonda district, Andhra Pradesh, India, to explore the causes of high fluorides in groundwater and surface water causing a widespread incidence of fluorosis in local population. The concentration of fluoride in groundwater ranges from 0.4 to 2.9 and 0.6 to 3.6 mg/l, stream water ranges from 0.9 to 3.5 and 1.4 to 3.2 mg/l, tank water ranges from 0.4 to 2.8 and 0.9 to 2.3 mg/l, for pre- and post-monsoon periods, respectively. The modified Piper diagram reflects that the water belongs to Ca 2+ –Mg 2+ –HCO 3 − to Na + –HCO 3 − facies. Negative chloroalkali indices in both the seasons prove that ion exchange between Na + and K + in aquatic solution took place with Ca 2+ and Mg 2+ of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water–rock interaction is responsible for major ion chemistry of groundwater/surface water. High fluoride content in groundwater was attributed to continuous water–rock interaction during the process of percolation with fluorite bearing country rocks under arid, low precipitation, and high evaporation conditions. The low calcium content in rocks and soils, and the presence of high levels of sodium bicarbonate are important factors favouring high levels of fluoride in waters. The basement rocks provide abundant mineral sources of fluoride in the form of amphibole, biotite, fluorite, mica and apatite.