The hydrogeochemistry of aquifers in the western Sokoto basin was assessed. The objective of this study is to identify the impact of geological variability on groundwater hydrochemistry and the mechanisms controlling the hydrochemistry of aquifers. Univariate statistics (several samples ANOVA), Pearson's (r), and multivariate statistics-hierarchical cluster analysis (HCA) and Factor analysis (FA) were used to interpret the hydrochemistry of aquifers. Subsequently, geochemical modeling was applied to assess the saturation index (SI) of rock minerals. Forty groundwater samples were collected from Gwandu (n = 20) and Illo (n = 20) formations. ANOVA results indicated that geological variability exerted a considerable impact on groundwater in Gwandu and Illo aquifers. It is characterized by a substantial amount of Ca 2+ , Mg 2+ , SO 4 2− , HCO 3 − , Na + , and K +. The hydrogeochemical facies indicated mixing conditions. FA and correlations analysis further revealed that groundwater received the noticeable influence of silicate weathering and dissolution of carbonates. There were significant differences in SI values for chrysotile, goethite, gypsum, H 2 (g), H 2 O(g), H 2 S(g), illite, and sepiolite minerals between the two geologic environments. Positive SI values for gibbsite were noticed in eleven sampling locations, indicative of potential recharge zones. Likewise, all the sampling locations have positive values for K-feldspar and are supersaturated with mica, suggesting both discharge and transition zones. The HCA classified aquifers into three clusters based on their hydrogeochemical characteristics. Geochemical modeling, univariate, and multivariate analyses are user-friendly tools for hydrochemical analysis.