Chamwino district, central Tanzania is a semi-arid granitic complex province, where groundwater is the major source of water for domestic and other uses. However, groundwater in the area is affected by salinity, thus, lowering the availability of potable water for various uses, decrease in crop production, taste less, wastage of soap, and abnormal pain. Due to this, this study sought to characterize groundwater using hydrogeochemical facies and signatures in order to identify the factors influencing the distribution of salt water in the Chamwino Granitic Complex. A total of 141 groundwater samples were collected from wells spatially distributed within the study area from January 2023 to April 2023, (a season of relatively low rainfall). All samples were subjected to in situ analyses of physicochemical parameters pH, temperature (T), total dissolved solids (TDS), electrical conductivity (EC), and salinity using a multi-parameter water analyzer and analyses of major ions (Ca2+, Mg2+, K+, Na+, Cl−, SO42−, HCO3−, and NO3−). The study revealed that the dominant cations in the groundwater are Na+ > Ca2+ > Mg2+, and the anions are Cl− > HCO3− > SO42. Five geological formations (granodiorite, tonalitic orthogenesis, migmatite, tonalite, and alluvium) were identified, and each is characterized by its unique groundwater facie. In the areas that are dominated with granodiorite, the major hydrogeochemical facies were Ca–HCO3, Na–Cl, Ca–Na–HCO3, Ca–Mg–Cl, and Ca–Cl water types; tonalitic orthogenesis was dominated by Ca–HCO3, Na–Cl, Ca–Mg–Cl, and Ca–Cl water types; migmatite was dominated by Ca–HCO3, Na–Cl, Ca–Mg–Cl, and Ca–Cl water types; tonalite was dominated by Na–Cl, Ca–Mg–Cl, and Ca–Cl water types; and alluvium was dominated by Na–Cl and Ca–Mg–Cl and Ca–Cl water types. The common hydrogeochemical facies in all five geological units are Na–Cl, Ca–Mg–Cl, and Ca–Cl water types. It is revealed that the groundwater in the study area is alkaline in nature and slightly saline with salinity level between 0.2 mg/L (fresh water) and 2.8 mg/L (brackish water) with mean 1.07 mg/L (of 141 samples). The factors controlling groundwater salinity distribution are mainly rock-water interaction and ion exchange reactions. Groundwater salinity in the study area is largely attributed to the abundance of Na+, Ca2+, Cl− and SO42−. Abundance of Na+ and Ca2+ is the results of both, weathering of feldspar minerals particularly plagioclase (Na–Ca feldspars) which are the major mineral in granites, and evaporation crystallization cycles of evaporates in semi-arid areas such as Chamwino. Also, such evaporation crystallization cycles account for the abundance of Cl− and SO42− especially in areas dominated by alluvium. However, anthropogenic activities as evidenced by elevated nitrate up to 212.6 mg/L in congested areas are also likely to contribute in area) to the elevated Cl− and SO42−. In other geological units such as tonalitic orthogneiss, migmatite and granodiorite, there was an ostensible mixing of saline water with fresh water from local recharge as indicated by the abundance of HCO3− ions. Nonetheless, the hydrogeochemical characterization of groundwater in the Chamwino granitic complex suggests that there is little possibility for groundwater to evolve to a carbonate water type (fresh water) because the groundwater salinity is mainly geogenic, unless artificial recharge through rainwater harvesting is applied.