A mesoporous MoO3/TiO2 composite was prepared from titanate derivative by consecutive self-supporting and ammonia method. All samples were characterized by X-ray Diffraction, N-2 adsorption-desorption, Raman Spectra and Field-Emission Scanning Electron Microscopy. The results showed that mesoporous MoO3/TiO2 composite had a higher surface area (173 m(2)/g) and a better MoO3 dispersion than that prepared by traditional impregnation (90 m(2)/g). As for hydrodesulfurization tests, mesoporous MoO3/TiO2 composite in this case presented a better catalytic performance, attributed to its high surface area and good dispersion of MoO3. It can be found that self-supporting played a key role in preparing mesoporous MoO3/TiO2 composite with high surface area. Additionally, aqueous ammonia could effectively dissolve excess MoO3, which helped to obtain mesoporous MoO3/TiO2 composite with better dispersion of MoO3.