Aji-Chay River is one of the most important surface reservoirs of northwest of Iran, because it passes through Tabriz city and discharges to Urmia Lake, one of the largest permanent salty lakes in the world. The main objectives of the present study are to evaluate its overall water quality and to explore its hydrogeochemical characteristics, including the potential contamination from heavy metals and metalloids such as Co, Pb, Zn, Cd, Cu, Cr, Al and As. For this purpose, 12 water samples were collected from the main river body and its tributaries within Tabriz plain. The Piper diagram classified water samples mainly into Na–Cl and secondary into Ca–HCO3 and mixed Ca–Mg–Cl types, denoting a profound salinization effect. The cross-plots showed that natural geochemical processes including dissolution of minerals (e.g., carbonates, evaporites and silicates), as well as ion exchange, are the predominant factors that contribute to fluvial hydrogeochemistry, while anthropogenic activities (industrial and agricultural) impose supplementary effects. Cluster analysis classified samples into two distinct clusters; samples of cluster B appear to have elevated electrical conductivity (EC) values and trace metals concentrations such as Co, Pb and Cd, while SiO2 and Zn are low in comparison with the samples of the cluster A. The main processes controlling Aji-Chay River hydrogeochemistry and water quality were identified to be salinization and rock weathering. Both are related with geogenic sources which enrich river system with elevated values of Na+, Cl−, Ca2+, Mg2+, K+, SO4 2− and EC as a direct effect of evaporites leaching and elevated values of Pb and Cd as an impact from the weathering process of volcanic formations. According to the US salinity diagram, all of the water samples are unsuitable for irrigation as having moderate to bad quality.