A series of CuCoZnAl-multicomponent mixed oxide catalysts with various Cu/Co atomic ratios were prepared by the thermal decomposition of CuCoZnAl-hydrotalcite (HT)-like precursors at 450 degreesC in static air atmosphere. The XRD of calcined materials revealed the formation of a mixture of CuO and ZnO, Co3O4, and/or ZnCo2O4 depending on the chemical compositions. Core-level XPS and X-ray induced Auger electron spectroscopy (AES) revealed unambiguously the existence of Cu2+, Co2+, and Co3+ species in the calcined materials. Upon H-2-reduction at 300 degreesC, the Cu2+ was reduced to a mixture of Cu+ and Cu-0, while Co3+ was reduced to Co2+. This was further supported by the in situ XRD of the reduced samples. Valence band (VB) photoemission studies demonstrated that the overlap between 3d bands of Cu and Co was marginal in calcined materials, however it was very high in the reduced samples. These mixed oxides were tested as catalysts in the oxidative steam reforming of methanol (OSRM) reaction for the production of H-2 in order to understand the effect of substitution of Co in the CuZnAl-oxide system. The Cu-rich catalyst, without Co, offered the highest H-2 production rate of about 200 mmol kg(-1) s(-1) with about 100% methanol conversion at 290 degreesC. Only trace amounts of CO were noticed. Introduction of Co decreased the H2 production rate as the Co-containing species favored the hydrogenation of CO/CO2 to CH4 under the reaction operating conditions.