Lowering the ignition temperature in partial oxidation of methanol (POM), an exothermic reaction, is important for further application in hydrogen fuel cell development. This study has clearly revealed that photo-triggered catalytic partial oxidation of methanol (photo-POM) over gold-promoted copper-zinc catalyst decreased ignition temperature in response to 2-10% increments of gold content. In particular, A(10)CZ (Au/Cu/ZnO catalyst with 10% Au, 30% Cu, 60% Zn) effectively reduced the ignition temperature (TO to room temperature and maintained 95% S-H2 (hydrogen selectivity) methanol oxygen mixtures (volume 2:1) under 200 W UV light with a wavelength of 377 nrn. During the ignition period, methoxy groups (-OCH3) were adsorbed onto the A(4)CZ surface, and then transferred to the intermediate formate state. The photo-generated electrons from ZnO were easily trapped by electronic acceptors, such as copper and gold, which was confirmed by in-situ X-ray absorption near-edge structure (XANES) spectra during photo-POM reaction. Gold also promotes the absorption of near UV light and significantly enhances the charge separation by extracting electrons from photo-excited ZnO, which consequently improves the photocatalytic activity at lower ignition temperature.