This study investigated the hydrogeochemical processes of groundwater in the Tasuj plain, Iran. The Tasuj plain is one of the 12 marginal plains around Urmia Lake which is currently under a critical ecological condition. In the last decades, the Tasuj plain aquifer suffered from severe groundwater level declination and caused degradation of groundwater quality. To better understand hydrogeochemical processes in the Tasuj plain, this study adopted graphical methods and multivariate statistical techniques to analyze groundwater samples. A total of 504 groundwater samples was obtained from 34 different locations (qanats, wells, and springs) over 12 years (1997–2009) and analyzed for 15 water quality parameters. From the results, the Piper diagram indicated four groundwater types and the Stiff diagram showed eight different sources of groundwater samples. The Durov diagram identified five major hydrogeochemical processes in the aquifer. However, hierarchical cluster analysis (HCA) identified five water types in the groundwater samples because HCA was able to analyze more chemical and physical data than graphical methods. The HCA result was checked by discriminant analysis and found consistency in all samples that were classified into correct groups. Using factor analysis, we identified three factors that accounted for 81.6% of the total variance of the dataset. Based on the high factor loadings of the variables, factors 1 and 2 reflected the natural hydrogeochemical processes and factor 3 explained the effect of agricultural fertilizers and human activities in the Tasuj plain. Dendrograms from 2000 to 2009 were studied to understand the temporal variation of groundwater quality. Comparing the distributions of groundwater types in 2000 and 2009, we found that the mixing zone was expanded. This may be due to artificial groundwater recharge in the recharge area and the effect of inverse ion exchange in the discharge area.