The corrosion and extraction toxicity of heavy metal in ancient smelting slag is analyzed. Leaching behavior of heavy metal in smelting slag is discussed through extraction toxicity test of different pH values. The results show that the pH of smelting slag is alkalescence, the heavy metal content is high and the average content of heavy metal (zinc plus plumbum) is up to 6.97%. However, most of heavy metal in smelting slag is in residual state. Its extraction toxicity is low and potential harm for environment is obviously weakened. It indicates that forecasting heavy metal’s potential harm for environment in smelting slag by totalizing method is not accurate. The leachable quantities of heavy metals significantly increase in extremely acidic and alkaline condition. The leachable quantities of Zn, Pb, Cr and Cd are all up to maximum when pH<3. The leachable quantities of Zn, Pb and Cr all increase when pH>12, but the extracting amount is lower than that in acidic condition. The leachable quantity of Zn, Pb, Cr and Cd is minimal in neutral condition. Under normal rainfall conditions, potential harm for environment of ancient smelting slag is decreased to a lower level. It can be treated according to the requirement for general industrial solid wastes.