The VOx-TiO2 (VT-RC) and sulfated VOx-TiO2 (VTS-RC) catalysts were prepared by rapid combustion method (RC) and evaluated by the one-step oxidation of methanol to dimethoxymethane (DMM). The results showed that the VT-RC and VTS-RC catalysts were consisted of nano-particles and exhibited pore structure. Compared with the coprecipitated VOx-TiO2 (VT-CP) catalyst, the VT-RC catalyst showed more acidic sites and stronger reducibility. The addition of sulfate into VT catalyst further increased the number of acidic sites and had little effect on the reducibility. The catalytic test showed that the VT-RC catalyst exhibited high DMM selectivity (89.96% at 35% methanol conversion), which was further increased on VTS-RC catalyst (91.76% at 48% methanol conversion), and that was due to the larger number of acidic sites and stronger reducibility on these catalysts.