The fractured groundwater aquifers, predominantly found in South Africa, show varying groundwater chemical characteristics in various locations. The hydrochemistry of groundwater is affected by the weathering of rock formations in contact and anthropogenic activities. Determination of groundwater chemistry is important for aquifer protection and overall groundwater management. A hydrochemical analysis is a useful tool for identification of water types, chemical composition, its suitability for specified purposes, and an important requirement for water use licensing applications. The hydrochemical data of groundwater from 79 boreholes near Leliefontein, Kamiesberg local municipality of South Africa, were analysed, using integrated statistical, geostatistics and spatial interpolation methods. The result shows Na+ and Cl− to be the abundant cation and anion. The mean concentration of Na at Leliefontein was 267.39 mg/l, and that of Cl was 574.81 mg/l. The ionic concentrations in groundwater was in sequence of Cl− > Na+ > HCO3− > SO42− > Ca2+ > Mg2+ > NO3− > Si > K+ > F-. The analysis indicated that the cation exchanges in groundwater are influenced by limited silicate weathering, with calcite and dolomite dissolution. Geostatistical and spatial analysis interpolation for the major cation (Na) and major anion (Cl), Sodium Adsorption Ratio (SAR), Electrical Conductivity (EC) and Water Quality Index (WQI) was performed using Inverse Distance Weighing method. The hydrochemical data for the Leliefontein groundwater were analysed to classify water for domestic use (drinking) and agriculture (irrigation) purposes, based on the recommended guidelines of the South African National Standard (SANS). The study area was characterised by high salinity of three water types, viz, Na-Cl seawater type, Ca-Cl reverse ion-exchange water type, and Na-HCO3 base ion-exchange water types. About 70–80% of the boreholes in Leliefontein met the requirement for irrigation application for Sodium Adsorption Ratio (SAR) and salinity hazard analysis, while the groundwater generally required further treatment before domestic use.