Copper and zinc oxide based catalysts prepared by coprecipitation were promoted with palladium and ZrO 2 , and their activity and selectivity for methanol oxidative reforming was measured and characterized by N 2 O decomposition, X-ray absorption spectroscopy, BET, X-ray photoelectron spectroscopy, X-ray diffraction, and temperature programmed reduction. Addition of ZrO 2 increased copper dispersion and surface area, with little effect on activity, while palladium promotion significantly enhanced activity with little change of the catalytic structure. A catalyst promoted with both ZrO 2 and palladium yielded hydrogen below 150°C. EXAFS results under reaction conditions showed that the oxidation state of copper was influenced by palladium in the catalyst bulk. A palladium promoted catalyst contained 90% Cu 0 , while the copper in an unpromoted catalyst was 100% Cu 1+ at the same temperature. Palladium preferentially forms an unstable alloy with copper instead of zinc during reduction, which persists during reaction regardless of copper oxidation state. A 100-h time on stream activity measurement showed growth in copper crystallites and change in copper oxidation state resulting in decreasing activity and selectivity. A kinetic model of the reaction pathway showed that palladium and ZrO 2 promoters lower the activation energy of methanol combustion and steam reforming reactions.