Silica is the main component of combustion-generated fly ash and is expected to have an important impact on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in municipal waste incinerators. In this work, we theoretically studied the reactions of 2-chlorinated phenol (2-CP) over the clusters (SiO(2))(3) and (SiO(2))(3)O(2)H(4), which mimic the dehydrated and hydroxylated silica structures, respectively. The dehydrated cluster is much more active toward the attack of 2-CP to form highly stable 2-chlorophenolate than the hydroxylated silica cluster. The further dissociation of chlorophenolates to form CP radicals (CPRs) is calculated to be very difficult. The calculated energy barrier of the reaction of 2-CP over the dehydrated (SiO(2))(3) cluster and IR data are in good agreement with early experimental observations. On the basis of the calculated results, we propose that the formation of PCDD/Fs from CPs over silica surfaces may not involve CPRs, but be relevant to the further conversion of chlorophenolates over Silica surfaces. This mechanism is very different from the corresponding reactions mediated by transition metal oxides. The result's presented here may be helpful to understand the chemisorption mechanism of CPs on silica surfaces in real waste combustion: