Dioxins and dioxin-like compounds released from municipal and industrial solid waste incinerators have been a serious problem from the viewpoint of environmental pollution control. Since these compounds are concentrated especially on fly ash, supplemental treatment systems to decompose/detoxify them are required after collecting the fly ash either by a bag filter or an electrostatic precipitator. The present work is aimed at developing a heat treatment technique for fly ash, which contains a large amount of calcium (Ca) derived from hydrated lime, at a temperature higher than 500 degrees C by adding chemical additives to prevent the solidification of Ca-rich fly ash. As calcium hydroxychloride (CaClOH) in the Ca-rich fly ash was found to cause solidification of fly ash at high temperatures, sodium hydroxide, mullite and coal fly ash were added as additives prior to the heat treatment. As a result, the additives studied in the present work are effective for decomposing CaClOH and therefore suppressing the solidification of fly ash, and yet they promoted the decomposition/detoxification of dioxins.