Hollow cubic TiO2 particles were synthesized using cubic Cu2O particles as hard templates, and the hydrolysis of tetrabutyl titanate (TBOT). The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-Vis spectrometer, respectively. The results show that the prepared TiO2 is composed of anatase TiO 2, and has a stronger absorption in the range of 300-400nm wavelengths in its UV-Vis spectroscopy. Experiments were carried out using a methyl orange solution as a model to evaluate the photocatalytic activity of hollow cubic TiO2 particles. The effects of catalyst dosage, initial concentration and pH of methyl orange solution on the degree of photodegradation have been investigated. It’s found that the hollow cubic TiO2 particles have a good photocatalytic property. And the degradation rate of the methyl orange, after methyl orange solution (5mg/L) containing hollow cubic TiO2 particles (0.5g/L) is irradiated by 125W ultraviolet light for 120 minutes, is 95%.