Pd-based catalysts modified with BaO as a promoter was prepared by impregnation method. The catalyst was characterized by H2-temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The catalytic activity towards methanol showed that the BaO modification promoted the conversion of methanol. The light-off temperature (T50), complete conversion temperature (T90) and ΔT (T90-T50) for methanol oxidation are 100°C, 125°C and 25°C, respectively. The H2-TPR results showed that the addition of BaO increased palladium highly dispersed and promoted the reductive ability. It also enhanced the metal-support interaction and increased the electronic surroundings of Pd and Ce sites, which maintained Pd in a higher oxidized state and Ce4+ in Ce3+ state, consequently increased the activity for methanol oxidation according to XPS measurements.