In the present study, formation of PCDD/Fs from carbon particles like soot', so called de novo synthesis, was experimentally simulated using the powder mixture of graphite and metallic chloride. Composite states of graphite and chloride particles were varied by the preliminary treatment, ie high-energy ball milling for different time or heating at different temperatures. These samples were subjected to the measurement of the rates of weight loss mainly due to the oxidation of carbon, the formation of absorbent organic chlorides (AOX) and the formation of PCDD/Fs at 300C. The amount of PCDD/Fs formation increased by applying certain pretreatments. Further, linear relationships were obtained among the formation rates of PCDD/Fs and AOX and the weight loss of sample. These results will give useful information to investigate the mechanism of PCDD/Fs formation from unburned combustible carbon and hydrocarbon in thermal processes.