Rock–water interaction along with mineral dissolution/ precipitation plays a profound role in the control of fluoride ion concentration within the alluvial groundwater in a part of semi-arid northern India. In the premonsoon season, the alluvial region experiences evaporative processes leading to increase in Na+ ions which through reverse ion exchange processes are adsorbed onto suitable sites within the aquifer matrix in exchange for Ca2+ ion in solution. Increase in Ca2+ ions in solution inhibits fluorite mineral dissolution, thereby controlling premonsoon fluoride ion concentration within alluvial groundwaters (1.40 ± 0.5 mg/l). In the postmonsoon season, however, higher average fluoride ion concentration within the alluvial aquifer samples (2.33 ± 0.80 mg/l) is observed mainly due to increase in silicate weathering of fluoride-bearing rocks and direct ion exchange processes enabling Ca2+ ion uptake from solution accompanied with the release of fluoride ions. Combined effect of these processes results in average fluoride ion concentration falling above the WHO drinking water permissible limit (1.5 mg/l). Alternatively, the hard rock aquifer samples within the study area have an average fluoride ion concentration falling below the permissible limit in both the seasons.