The synthesis of dimethoxymethane (DMM) from direct oxidation of dimethyl ether (DME) is a green and competitive route with good atomic economy and low carbon emission and is also an urgent need. In this work, biomass-based carbon-supported sulfate catalysts were designed and prepared for the efficient synthesis of DMM from DME oxidation. The prepared carbon support from cellulose displayed much larger specific surface area and a developed microporous structure, which effectively benefited a high dispersion of sulfate components, leading to mainly weak acid sites and more oxygen functional groups on the catalyst surface. The Ti(SO4)2/PC-H2SO4 catalyst exhibits excellent performance for DME oxidation with DMM1-2 selectivity up to 96.7%, and DMM selectivity reaches 89.1%, notably higher than that of previously reported results. The distinctive surface structure and chemical properties of the carbon support have important impacts on the dispersion state of sulfate species, affecting the acidic and redox properties of the catalysts.