Heavy metals and As (HMs) pollution in mining areas are a widespread environmental concern. In this study, ground water, surface water, and sediment samples around the Dexing area, one of the largest Cu-polymetallic ore clusters in China, were collected to examine the concentrations and distributions of As, Cd, Cr, Cu, Hg, Pb, and Zn. Pollution indices, geo-accumulation index, and potential ecological risk index were used to estimate the pollution characteristics and ecological risk of HMs. The results show that the major pollutants in the surface water were Cd, Cu, Zn, and Pb, while the dominant ecological risk of HMs in the sediments originated from Cu, As, Hg, and Cd. Moreover, HMs in the surface water and sediments exhibited substantial spatial heterogeneity in the study area, indicating a severely disturbed environment due to mining activities. The proportions of HM pollutions were higher in the Dexing River and its tributaries than in the Le’an River and its tributaries. The surface water pollution was predominant at the tributaries closest to the mine area, while the sediment contamination has been expanded several kilometers downstream of the major rivers. Overall, the ecological risk of HMs was higher in the sediments than in the surface water.