The objective of this study was to evaluate the formation characteristics of CBs and CPs from TCE, aliphatic compound. The experiment was carried out in a fixed reactor during 30 min under the oxidation condition at the range of temperature, 300~$700^{circ}C$. MSWI fly ash was used as catalyst in this study. Total amount of CBs formed greater magnitude than that of CPs overall range of reaction temperature. It is proposed that the formation of CPs was caused from hydroxylation of CBs. According to increasing temperature to $600^{circ}C$, the yield of CBs and CPs increased but significantly decreased at $700^{circ}C$. It is suggested that decomposition rate was faster than formation rate at the high temperature. In the homologue distribution of CBs, DCBs were major products at 30$0^{circ}C$ and the amount of higher chlorinated compound increased to $600^{circ}C$. Because they were formed by chlorination of lower chlorinated compounds. In case of CPs, the amount of DCPs was 90% of total amounts in both thermal formation and catalytic reaction. On the other hand it was clearly observed that the chlorination rate in catalytic reaction was higher than in thermal formation with TCE only.