Metal oxides, such as copper (II) oxide (CuO) and iron (III) oxide (Fe2O3), are dominant active components in fly ash during iron ore sintering. The potential synergetic effects of these oxides on the formation of chlorobenzenes (CBzs), polychlorinated biphenyls (PCBs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were investigated based on in situ XPS analysis. Besides, the effect of trace metals, such as lead (II) oxide (PbO) and manganese (II) oxide (MnO) (0.5 wt.%), were also studied. The results demonstrated that CuO and Fe2O3 showed synergetic effect on the formation of chlorinated aromatics at a Cu/Fe mass ratio of 10:1. The in situ XPS results indicated that the synergistic effect of CuO and Fe2O3 with a Cu/Fe mass ratio of 10:1 might be attributed the enhanced oxidation and chlorination of carbon, contributing to a much higher production of CBzs, PCBs and PCDD/Fs. In addition, the quantities of polychlorinated dibenzofurans (PCDFs) were correlated linearly with those of CBzs and PCBs, which suggests the potential of CBzs and PCBs as indicator compounds for predicting PCDD/Fs emissions. Furthermore, the addition of PbO promoted the formation of CBzs while the yield of CBzs and PCBs decreased slightly after addition of MnO to the SFA.