The V2O5/TiO2 catalysts were prepared by improved rapid sol-gel method and the catalytic behavior for dimethoxymethane(DMM)synthesis from methanol selective oxidation was investigated.The physicochemical properties of catalysts were characterized by XRD,BET,Raman,XPS,H2-TPR,NH3-TPD,Py-IR,SEM and TEM techniques.The particle size of catalyst was about 5-6nm.The catalysts behaved loose structure and showed higher surface area.Studies showed that the catalysts prepared by the improved rapid sol-gol method achieved behaved high activities for methanol selective conversion to DMM.When V2O5 content was 10wt%,the catalyst displayed best activity in the methanol direct selective conversion to DMM,giving about 45.62%conversion of methanol and 98.67%selectivity to dimethoxymethane at 423K.Furthermore,the catalyst exhibited good reaction stability for methanol oxidation to DMM within 240h.Results showed that proper acidic sites and higher vanadium disperse on the surface of the catalysts facilitated the catalytic performance.