Sequential extraction method was employed to study the heavy metals concentration and form change during aerobic high temperature compositing of pig manure, and the effects of amendment with different proportion of passivators on the concentration and form change. During the composting process, the concentrations of total As, Cu, and Zn in the manure all increased to some extent. As for the form change of the heavy metals, the exchangeable As and Zn decreased while the residual As and Zn increased, indicating that the availability of As and Zn declined through the composting process. On the other hand, the exchangeable and residual Cu decreased while the carbonate-, Fe/Mn-, and organic bound Cu increased, suggesting the potential environmental risk of the future application of the compost. Among the passivators amended, 5.0% of sepiolite and 2.5% of bentonite had the best effect in reducing the availability of As and Zn, with the residual form of As and Zn after composting increased by 79.8% and 158.6%, respectively, and 7.5% of sepiolite induced the least decrement (39.3%) of residual Cu, compared with the control. Therefore, amendment with appropriate proportion of passivator during pig manure composting could decrease the availability of heavy metals in the manure, and reduce the environmental risk of applying the compost to farmland.