Groundwater under Basement Complex areas of southern Kebbi has been characterized in order to determine its suitability for drinking and irrigation use. Water samples were drawn from shallow groundwater (hand-dug shallow wells < 5 m) and deep groundwater (boreholes > 40 m). Physical parameters (i.e., temperature, TDS, pH, and EC), were determined in situ, using handheld meters. Discrete water samples were obtained for determination of chemical parameters. Results from severalsample ANOVA (Kruskal-Wallis test) suggested that heterogeneity in water table appeared to exert significant influence on groundwater chemistry which is characterized by a significant difference in pH, EC TH, Na + , Zn 2+ , Mg 2+ , PO 4 3− , Cl − , HCO 3 − , SO 4 2− , and NO 3 − concentrations. Also, ions including Fe 3+ , Zn 2+ , Mg 2+ , Na + , PO 4 3− , and SO 4 2− are above World Health Organization (2011) and National Standard for Drinking Water Quality (2007) reference guidelines. Most of the groundwater sources are moderately hard. Groundwater classification based on chloride, EC, and TDS revealed water of excellent quality for all types of uses. However, groundwater classification based on nitrate pollution revealed water of poor quality. Rock mineral is the major mechanism controlling water chemistry, as revealed by the Gibbs model. Most of the water sources have positive Scholler index, indicative of overall base exchange reactions in the underlying aquifers. Such condition was well explained by Piper trilinear diagram, which revealed two types of faces: Ca-Mg-HCO 3 and Ca-Mg-SO 4-Cl. The HCA categorized wells into three groups according to their hydrogeochemical physiognomies. Despite the significant difference in ions concentration and chemical indices, groundwater composition is more influenced by rock weathering than anthropogenic inputs. Groundwater evaluation for irrigation use indicates a significant difference in SAR level which is related to poor permeability index in shallow groundwater. Higher values of Kelly's index and magnesium adsorption ratio threatened groundwater suitability for irrigation use in the study area.