A study was carried out of the hydrogeochemical processes involving the groundwater of the western portion of the Santa Maria Aquifer System (SMAS) in the central region of Rio Grande do Sul. The objective of this study was to characterize the behavior of a portion of the groundwater between São Pedro do Sul, Santa Maria and Restinga Seca municipalities, based on a model between water/rock interaction. Mineralogical and hydrochemical information were analyzed, aiming to model the hydrogeochemical evolution of the aquifer in these municipalities. For this purpose, a processing of the information in a geochemical modeling code was performed, using as previous reference mineralogical studies. The results pointed out the main geochemical interactions responsible for groundwater chemistry, which is strongly dependent of the chemical composition of the recharge waters and the mineralogical contribution of the sedimentary rocks of this aquifer system. The groundwater saturation states showed subsaturation processes tending to the balance of carbonate minerals, indicating the dissolution of these minerals, mainly calcite, as well as supersaturation of clay-minerals ilite, montmorillonite (smectite) and kaolinite, in both cases tending to the alkalinization of the environment. The characterization of the hydrogeochemical properties of aquifers is important for a correct understanding of the processes that occur in it and dominate the regional hydrogeology.