The effect of water vapor on catalyzed de novo formation of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) was investigated through experiments conducted on a fixed-bed apparatus. The results indicated that water vapor could promote the formation of PCDD and PCDF. The dominant pathway was activating fly ash in this work, while water also reacted with chlorine to change the equilibrium of Deacon reaction, which influenced the final yield of PCDD/PCDF. Also a suppression effect of water on CuCl(2) was found according to the values of the catalysis indicator. It is possible that water reduced the catalysis of CuCl(2) or prevented its direct chlorination. But the overall effect of water on the formation of PCDD and PCDF was promotion rather than inhibition.