Chlorides derived from plastics and food residue content in MSW will affect the formation and partitioning of metal chlorides in the incineration discharges. Our study investigated the effects of waste-derived chlorides on the partitioning of heavy metals in a single-metal combustion system. The results indicate that the heavy metal partitioning behaviors are mainly affected by the presence of chloride, alkaline metals (i.e., Na, K) and moisture in the wastes. The configuration of the metal partitioning is determined by the availability of chlorine, hydrogen, and alkaline metals, or the extent to which the elements may divide from their compounds at a given combustion temperature. The effects of chlorides, including PVC, C2Cl4, FeCl3, NaCl and KCl, were also discussed.