Mixed oxides composed of Zn-Sn, Ti-Sn and V-Sn were prepared by a co-precipitation method and evaluated as catalysts for methanol oxidation in an ambient fixed-bed reactor. Surface analysis by X-ray photoelectron spectroscopy (XPS) revealed an electronic interaction between dopant and Sn atoms in the oxide structure and showed the formation of surface states associated with the dopants. Oxygen vacancies were present on the Zn-doped oxide, and the oxidation of methanol to carbon oxides was favored. The Ti-doped oxide exhibited a favorable selectivity to dimethyl ether, related to the oxygen anions near Ti centers. Vanadium dopants not only dramatically increased the catalytic activity but also promoted the partial oxidation of methanol to formaldehyde. Results demonstrate that the bridging dopant-O-Sn bond acts as active sites and influences product distribution. (C) 2010 Elsevier B.V. All rights reserved.