A series of Ba-modified MnCeOx/TiO2 catalysts were prepared by a wet impregnation method and tested for selective catalytic reduction (SCR) of NO with NH3 at low temperature. The results showed that Ba additives obviously improved the catalytic performance of the MnCeOx/TiO2 catalyst for NH3-SCR, and the BaMnCeOx/TiO2 catalyst with 3 wt% BaO exhibited the optimal catalytic performance. Moreover, the introduction of Ba also improved the resistances toward water vapor and SO2 of catalysts. The N2 adsorption, H2-TPR, and X-ray photoelectron spectroscopy results showed that the addition of Ba increased the specific surface area, redox properties, and concentrations of surface Mn4+ and chemisorbed oxygen of catalysts. Furthermore, NH3-TPD and NO-TPD were used to investigate the absorption of NH3 and NO on the catalyst. The results revealed that although the introduction of Ba significantly promoted the adsorption of NO, it also inhibited the adsorption of NH3. Consequently, the catalytic performance of MnCeOx/TiO2 was greatly improved with the Ba additives.