TiO2/TiB2 heterostructures were successfully synthesized by a facile hydrothermal approach in an aqueous solution of hydrogen peroxide (H2O2). The influence of H2O2 on TiB2-based materials was systematically investigated using X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that TiB2 is prone to oxidize in the presence of H2O2. TiO2/TiB2 heterostructure which high-density anatase-TiO2 stand on the surface can be gained in the presence of H2O2 solvent and the final composition can be controlled by the temperature and time. The investigation may provide a path to further understand the chemical property of TiB2-based materials and synthesis method of heterostructure.