A new route to synthesis hierarchical Ti-rich TS-1 with uniform intracrystalline mesopores, uniform crystal size and the higher Ti content has been developed by using the environmental-friendly and cheap surfactant Triton X-100 as the assisted template agent and (NH4)(2)CO3 as crystallization-mediating agent. In this way, the surface area and pore volume of the resulting materials can be adjusted by the Triton X-100 content. The catalytic properties of the Nano-size hierarchical Ti-rich TS-1 were investigated by hydroxylation of benzene to phenol with H2O2 as oxidizing agent and deionized water as solvent. Due to the combination of hierarchical pores and high titanium content, the hierarchical Ti-rich TS-1 shows improved catalytic activity in the oxidation of benzene. [GRAPHICS] .