Ramanathapuram is a drought-prone southern Indian district that was selected for conducting a hydrogeochemical study. Groundwater samples from 40 locations were collected during January 2020 (pandemic interdiction according to COVID) and January 2021. The hydrogeochemical properties of the groundwater samples were evaluated and compared with drinking water regulations to assess their water quality. The order of cation dominance was as follows: Na+ > Ca2+ > K+ > Mg2+ in January 2020 and Na+ > Ca2+ > Mg2+ > K+ in January 2021 with respect to the mean value. The order of anion dominance was as follows: Cl− > HCO3− > SO42− > NO3− > F− in January 2020 and Cl− > SO42− > HCO3− > NO3− > F− in January 2021 with respect to the mean value. In the study area, the southern coastal region was identified as a groundwater-polluted zone through spatial analysis based on all analysis results. The irrigation water quality was analyzed using various calculated indices, such as Na% (percent sodium), SAR (sodium absorption ratio), PI (permeability index), MgC (magnesium risk), RSC (residual sodium concentration), and KI (Kelly ratio), demonstrating the suitability of the groundwater for irrigation in most parts of the study area. This was also confirmed by the Na% vs. EC Plot, USSL, and Doneen’s Plot for PI. In addition, the WQI results for drinking water and irrigation confirmed the suitability of the groundwater in most parts of the study area, except for the coastal regions. The dominant hydrogeologic facies of Na+-Cl−, Ca2+-Mg2+-SO42−, and Ca2+-Mg2+-Cl− types illustrated by the Piper diagram indicate the mixing process of freshwater with saline water in the coastal aquifers. Rock–water interaction and evaporation were the main controllers of groundwater geochemistry in the study area, as determined using the Gibbs plot. Ion exchange, seawater intrusion, weathering of carbonates, and the dissolution of calcium and gypsum minerals from the aquifer were identified as the major geogenic processes controlling groundwater chemistry using the Chadha plot, scatter plot, and Cl−/HCO3− ratio. Further, multivariate statistical approaches also confirmed the strong mutual relationship among the parameters, several factors controlling hydrogeochemistry, and grouping of water samples based on the parameters. Appropriate artificial recharge techniques must be used in the affected regions to stop seawater intrusion and increase freshwater recharge.