Highly ordered mesoporous WO3(χ)-CeO2 have been successfully synthesized. The ordered mesoporous WO3(χ)-CeO2 shows superior low temperature catalytic activity and N2 selectivity. The ordered mesoporous WO3(χ)-CeO2 have stronger Lewis acid sites and higher Ce3+ concentration. The ordered mesoporous WO3(χ)-CeO2 also presented excellent H2O resistance and alkali metal resistance.