Copper-zinc-aluminum (CZA) catalysts prepared by the homogeneous precipitation of chloride salts in the presence of urea to produce hydrogen selectively by partial oxidation and oxyreforming reactions of methanol were used. The crystalline phases of the precursors and of the air-calcined CZA samples were identified by X-ray diffraction. Temperature-programmed reduction revealed that both CuO and CuAl2O4 phases were present in the calcined catalysts. Prereduced catalysts were tested in both partial oxidation (O-2/CH3OH = 0.3-0.4) and oxyreforming reactions (O-2/CH3OH/H2O = 0.3 : 1 : 1.1) of methanol exhibiting high activity for CH3OH conversion and very high selectivity for H-2 production. The product distributions obtained in the partial oxidation of methanol (POM) reaction as a function of CH3OH and O-2 conversion indicate clearly that both conversion and selectivity become strongly dependent on the O-2 concentration in the gas phase and much less on the catalyst composition investigated. At low methanol conversion, when O-2 is not completely consumed, combustion and decomposition of methanol are the dominant reactions, however when O-2 is near or completely consumed, the methanol conversion goes beyond the expected stoichiometric POM values (60 and 80% for O-2/CH3OH molar ratios of 0.3 and 0.4, respectively). For the oxyreforming reaction, the simultaneous increase in H-2 selectivity at the expense of water, with a less marked increase of CO selectivity, points to the contribution of steam reforming of methanol. The Auger parameter of copper of the catalysts used in the partial oxidation (1849.1 eV) and in the oxyreforming (1849.3 eV) reactions indicates that Cu2O species are present on the active catalyst surface. These Cu2O structures, developed on the catalyst surface during on-stream operation, appear to be sufficiently large to be also observed by X-ray diffraction of the catalysts used in both reactions.