The selective oxidation of methanol to dimethoxymethane (DMM) was performed over a series of binary vanadia-based oxides (V2O5-TiO2, V2O5-ZrO2, V2O5-Al2O3 and V2O5-CeO2)and the corresponding sulfated catalysts. The physicochemical properties of catalysts were characterized by BET, Raman, XPS, TPR-MS, ammonia adsorption calorimetry and sulfate TPD-MS techniques. The strength of the sulfate-support interaction depends on the nature of the oxide support and increases in the following order CeO2 > Al2O3 > ZrO2 > TiO2. The catalytic reactivity was correlated with the nature of V-O-support bonds. Sample V2O5-TiO2 exhibits the highest intrinsic activity of methanol oxidation. With the addition of sulfate, the selectivity to DMM was enhanced whereas the turnover frequency (TOF) value of vanadium sites decreased, with a rate depending on the strength of sulfate-support bonds. The best catalyst (V2O5-TiO2 SO) with higher DMM yield presented higher reducibility, proper acidity and moderate strength of sulfate species. (C) 2010 Elsevier Inc. All rights reserved.