This paper reports the results of higher F − and HCO − 3concentrations and its response to high pH level in a hard rock terrain in Tamil Nadu, India. About 400 groundwater samples from the study area were collected from a period of four different seasons and analysed for F − , HCO − 3and other major cations and anions. The key rationale for the higher fluoride and bicarbonate in the study area is the soaring rate of the leaching fluoride-bearing minerals and weathering processes. Fluoride and HCO is linearly correlated with F − which indicates that these ions were consequent from the weathering influences. At the same time, poor correlation of F − with pH could possibly be due to the increase of alkalinity follow-on from the swell of bicarbonate level with very low Ca 2+ that promotes increase in F − concentration in the groundwater.