The methanol decomposition reaction was studied over model film catalysts of Pd simultaneously deposited with three different oxides (SiO2, Al2O3 and ZrO2) on quartz basal plates in a vacuum chamber. PVD mixing of Al2O3 and ZrO2 with Pd enhances the catalytic activity of values of Pd for methanol decomposition. Although the activity of Te PVD catalysts were different for different mixing supports, the Pd3d XPS spectrum showed almost the same peaks and shapes among the combinations with SiO2, ZrO2 and Al2O3. Also almost no desorption of CO on these active catalysts was observed at the reaction temperature in the CO-TPD experiment in the presence of hydrogen. On the other hand, the highly active catalysts show high binding energy of Ols XPS peaks. The reason for activity change with supports is thought to be that the reaction fields around Pd particles are changed by the support.