A high concentration of fluoride (F⁻) in drinking water is harmful and is a serious concern worldwide due to its toxicity and accumulation in the human body. There are various sources of fluoride (F⁻) and divergent pathways to enter into groundwater sources. High F⁻ incidence in groundwater was reported in Raigarh district of Central India in a sedimentary (Gondwana) aquifer system. The present study investigates the hydrogeochemistry of groundwater in the Tamnar area of Raigarh district to understand the plausible cause(s) of high F⁻ concentration, especially the source(s) and underlying geochemical processes. Groundwater samples, representing pre-monsoon (N = 83), monsoon (N = 20), and post-monsoon (N = 81) seasons, and rock samples (N = 4) were collected and analyzed. The study revealed that (i) groundwater with high F⁻ concentration occurs in the Barakar Formation, which has a litho-assemblage of feldspathic sandstones, shales, and coal, (ii) high F⁻ concentration is mainly associated with Na-Ca-HCO₃, Na-Ca-Mg-HCO₃, and Na-Mg-Ca-HCO₃ types of groundwater, (iii) the F⁻ concentration increases as the ratio of Na⁺ and Ca²⁺ increases (Na⁺: Ca²⁺, concentration in meq/l), (iv) F⁻ has significant positive correlation with Na⁺ and SiO₂, and significant negative correlation with Ca²⁺, Mg²⁺, HCO₃⁻, and TH, and (v) high F⁻ concentration in groundwater is found in deeper wells. Micas and clay minerals, occurring in the feldspathic sandstones and intercalated shale/clay/coal beds, possibly form an additional source for releasing F⁻ in groundwater. Feldspar dissolution coupled with anion (OH⁻ or F⁻) and cation (Ca²⁺ for Na⁺) exchange are probably the dominant geochemical processes taking place in the study area. The higher residence time and temperature of groundwater in deeper aquifers also play a role in enhancing the dissolution of fluorine-bearing minerals. Systematic hydrogeochemical investigations are recommended in the surrounding area having a similar geologic setting in view of the potential health risk to a large population.