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LaFeO3 is a perovskite structure (ABO3) catalytic and p-type semiconductor sensing material, its sensing property for toxic gases is seldom reported. The nanocomposites of LaFeO3 and LaFe1-xMgx O3 (x = 0.02, 0.04, 0.06) were prepared by solution based method and their crystal structures were characterized by X-ray diffraction (XRD). The sensing test results showed that the response of LaFeO3 to NO2 is greatly enhanced by surface modify of MgO from the former 11.90 increased to 891 at the optimum operating temperature of 350°C, and could be contributed to increase of surface active sites supplied by MgO for both oxygen and NO2 adsorption and surface reaction. The effect of MgO loading and chemical state on gas sensing have been investigated by temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopic (XPS) analysis.