Chlorine, sulfur and phosphorus were selected as element donators to investigate their effect on the volatilization behavior of heavy metals in sludge sewage incineration. Principal component analysis indicated that the promotive effect on the volatilization of heavy metals was followed by chlorine, sulfur and phosphorus. This result was proved to be correct by total release of heavy metals in sewage sludge incineration using different element donators. The release of heavy metals was very chlorine dependent, especially cadmium (Cd), lead (Pb) and nickel (Ni). When chlorine content was in the range of 0.1–0.5wt%, the increase of the volatilization rate was 44.9% for Cd, 6.8% for Pb and 4.6% for Ni, respectively. Although sulfur contributed to the promotion of the volatilization of heavy metals, excess oxygen impaired the promotive effect of sulfur on the release of heavy metals from the condensed phase. For phosphorus, solidifying heavy metals was dominant. Energy analysis showed that metal chlorides and sulfides were prone to volatilize or to be decomposed at elevated temperature compared with sulfates and phosphates owing to low binding energy in absolute value (V_LFA). It was the difference of binding energy that led to the different volatilization behavior of metal compounds in a high temperature, oxygen-enriched atmosphere.