In this study, the water quality of the Marreco River in the municipality of Toledo, PR, Brazil was investigated as part of a monitoring program. Conventional water pollution parameters (pH, turbidity, conductivity, COD, DO, ammonia, and total phosphorus) and metal elements were analyzed. Acute toxicity bioassays were conducted by the bacterial bioluminescence method, using the indicator Vibrio fischeri to evaluate the toxic effect of the contaminants. Principal components analysis (PCA) and Pearson’s correlation were applied to assess the statistical correlation between the physicochemical parameters and metals in the water samples. There is strong evidence, supported by Pearson and PCA analyses, of the presence of elevated levels of K and Ca associated with anthropogenic activities installed in the river basin.