Ag/Al2O3 catalyst with 5% Ag loading was prepared by the single step sol-gel mixture method and the effects of adding SO2 to reaction feed on NO reduction by CH3OH over the catalyst was investigated in the presence of oxygen. The results showed that in the absence of SO2 and H2O the catalyst displayed lower activity temperature and higher N2O selectivity, which was attributed to the partial reduction of oxidized Ag into metallic Ag under reaction conditions. Selective catalytic reduction activity was not decreased but significantly increased, N2O formation was suppressed and most effective NO reduction temperature shifted to higher temperature by pre-sulfated Ag/Al2O3 or addition of SO2 to reaction mixture. XPS analysis showed that the sulfate-like species were formed by the effect of SO2.