Abstract: The synthesis of methyl formate (MF), dimethoxymethane (DMM) and polyoxymethylene dimethyl ethers (PODE_n) from methanol can not only extend the methanol industry chain and digest the large surplus production capacity of methanol, but also bring on enormous benefits in respects of economic development and environmental protection. As a result, it has attracted extensive attention in recent years and great progresses have also been made in the research and development of efficient catalysts and production processes. This paper attempts to make a review on the recent research progresses in the catalytic synthesis of MF, DMM and PODE_n from methanol, in the aspects of developing efficient catalysts and exploring the catalytic reaction mechanism. Especially, the review focuses on the selective oxidation of methanol to MF over noble metal catalysts, the selective oxidation of methanol to DMM over vanadium-based catalysts, and the synthesis of PODE_n from trioxymethylene (TOM) with methanol or DMM over acidic zeolite catalysts. Lastly, an outlook is given on the possible trends in the development of new efficient catalysts and processes to acquire methanol-down-stream products with high value.