Surface state and reactivity of vanadium-tin mixed oxide nanoparticles (V/Sn ratios 0.05-0.2) were characterized by spectroscopic techniques and catalytic measurements. Analyses by X-ray photoelectron spectroscopy (XPS) and diffuse reflectance spectroscopy (DRS) revealed that the oxidation state and surface structure of vanadium oxide species and the electronic interaction between Sn and V atoms are dependent upon the vanadium content. These oxides were evaluated as catalysts for methanol oxidation in a fixed-bed reactor. Both reaction rate and formaldehyde selectivity increased with increasing the vanadium amount in catalyst. Results demonstrate that the V5+ site in the bridging V-O-Sn structure exhibits a high redox activity to facilitate the transformation of adsorbed methoxy to formaldehyde and that the vanadium dispersion plays a crucial role in the surface reactivity. A mechanism that elucidates the catalytic redox process is proposed. (C) 2011 Elsevier B.V. All rights reserved.