The synthesis and application of bifunctional mesoporous Al-P-VO catalysts with both acidic and redox sites for selective oxidation of methanol to dimethoxymethane (DMM) is described. The catalysts were characterized by N2 adsorption/desorption, X-ray diffraction, temperature-programmed desorption, X-ray photoelectron spectroscopy, and infrared spectroscopy. It is shown that porosity; redox property and surface acidity of the catalysts were greatly influenced by the Al/V/P ratio. The synergistic effect of phosphorus and vanadium was investigated. Al-P-VO catalysts exhibited good catalytic activity because of the controlled reducibility and the acidic sites. (c) 2013 American Institute of Chemical Engineers AIChE J, 59: 2587-2593, 2013