This study explores the utility of silica concentration in deciphering geological controls and hydrogeochemical processes affecting groundwater quality in Mount Cameroon’s volcanic terrain. Fifty water samples from wells, boreholes, springs, and rivers were analysed for hydrochemical properties (EC, pH, temperature, TDS) and major ion concentrations (Ca2+ > Mg2+ > K +> Na+ and HCO3− > Cl −> NO3− > SO42−). The groundwater exhibits low mineralization, with a dominance of Ca2+, Mg2+, HCO3−, and SiO2, reflecting minimal water–rock interaction and short residence times. Spatial variations in hydrochemistry suggest diverse water–rock interactions and potential mixing processes (76% of samples in rock dominance zone). Silica concentrations (5.8–58.7 mg/L) and estimated chalcedony temperatures (> 60 ℃ at five sites) indicated depths exceeding 1000 m. This research highlights silica’s effectiveness in tracking water–rock interactions across diverse geological settings, regardless of flow depth or interaction time variations. Mineral saturation indices pointed towards supersaturation with silicate minerals (quartz) but undersaturation with carbonates, sulphates, and halides. These findings contribute to a better understanding of groundwater evolution in Mount Cameroon, valuable insights into the hydrogeochemical processes shaping groundwater quality, aiding sustainable water resource management practices that can benefit local communities by ensuring a reliable source of freshwater. However, opportunities exist to improve future studies and water resource management. For a more comprehensive understanding, future analyses should include a broader range of geochemical tracers, such as nitrate (NO3−) and phosphate (PO43−), to assess potential agricultural or anthropogenic contamination. The study also found elevated levels of chloride and sodium, suggesting potential anthropogenic influences on groundwater quality, such as agricultural practices and waste disposal.