The rapid high temperature (580-680 degrees C) formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the heterogeneous bed region of a spouted bed combustor occurred within fraction of seconds (0.1-0.2 seconds) using two different precursors; 1,2-dichlorobenzene and 2,4-dichlorophenol Levels of PCDD/Fs produced from 2,4-dichlorophenol oxidation were two orders of magnitude higher than those produced from 1,2-dichlorobenzene, indicating that the high temperature PCDD/Fs formation rate is much faster from chlorophenol precursors. In agreement with typical incinerator observations, the PCDDs to PCDFs ratios were less than one under all conditions. Modeling calculations were performed using gas phase mechanisms for the formation of PCDDs with chlorophenols as precursors, under the conditions existing in the high temperature bed legion. A semi-empirical surface-mediated model is suggested for estimating the formation of PCDDs from chlorophenols.