The development of fast and high yield route for large scale synthesis porous TiO2 based catalyst has attracted widespread concern in the field of optoelectronic and catalysis. Up to now, the facile synthesis of mesoporous TiO2 based composite is still limited to wet chemical synthesis approach (hydrothermal, phase transformation, or sol-gel method etc.). Here, we develop a polyethyleneimine-assisted solvent-free strategy to synthesize of ionic liquid-derived Mo-based mesoporous TiO2 composite, with molybdenum sites uniformly distributed on TiO2 matrix. As-synthesized ionic liquid-derived mesoporous MoOx/TiO2 composite is composed of uniform nano-sized anatase particles and connected by worm-like mesoporous channel. Moreover, the calcination conditions and loading amount of molybdenum-containing ionic liquid have been further optimized. These distinct characteristics endow the prospective MoOx/TiO2 composite with excellent performance in catalytic oxidation reaction, which can remove refractory organic sulfur compound in the model fuel effectively. Our work opens a new solvent-free avenue to synthesis porous metal based ionic liquids/TiO2 composite.