This study reports multivariate statistical techniques applied including cluster analysis to evaluate and classify the river pollution level in Taiwan, and principal component analysis-multiple linear regression (PCA-MLR) to identify the possible pollution source. Water quality and heavy metal monitoring data from Taiwan Environmental Protection Administration (EPA) was evaluated for 14 rivers in the four regions of Taiwan. The Erren River was classified as the most polluted River in Taiwan. Biochemical oxygen demand, ammonia, and total phosphate concentration in this river were the highest of the 14 rivers evaluated. In addition, heavy metal levels of the following rivers exceeded the Taiwan EPA standard limit: lead - in the Dongshan, Jhuoshuei, and Xinhuwei Rivers; copper - in the Dahan, Laojie, and Erren Rivers; and manganese - in all rivers. Water pollution in the Erren River was estimated to originate 72% from industrial sources, 16% from domestic black water, and 12% from natural sources and runoff from other tributaries. Our research showed that PCA-MLR and the cluster analysis model accomplished our study objectives and will be helpful tools to evaluate water quality in rivers and we suggest that the continuous monitoring should be conducted to monitor water pollution from anthropogenic activities.