A better understanding of exposure to and effects of copper-rich pollutants in soils is required for accurate environmental risk assessment of copper. A greenhouse experiment was conducted to study copper bioavailability and bioaccumulation in agricultural soils spiked with different types of copper-rich mine solid wastes (copper ore, tailing sand, smelter dust, and smelter slag) and copper concentrate. A copper salt (copper sulfate, CuSO4) that frequently is used to assess soil copper bioavailability and phytotoxicity also was included for comparison. Results showed that smelter dust, tailing sand, and CuSO4 are more likely to be bioavailable and, thus, toxic to plants compared with smelter slag, concentrate, and ore at equivalent total copper concentrations. Differences may be explained by intrinsic differences in copper solubilization from the source materials, but also by their capability to decrease soil pH (confounding effect). The copper toxicity and bioaccumulation in plants also varied according to soil physicochemical characteristics (e.g., pH and total organic carbon) and the available levels of plant nutrients, such as nitrogen, phosphorus, and potassium. Chemistry/mineralogy of mine materials, soil/pore-water chemistry, and plant physiological status thus should be integrated for building adequate models to predict phytotoxicity and environmental risk of copper.