TiO2 nanospheres with hollow structure were obtained by a facile hydrothermal process at the temperature of 200°C. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), Raman spectrum (Raman), UV–Vis absorption spectroscopy (UV–Vis) and fluorescence spectra (FL) were used to characterize the samples, and the photocatalytic activity of the products was tested by the degradation of rhodamine B under the UV light. The formation of this hollow structure in samples prepared at 200°C can be interpreted as the preferential dissolution of the internal structure which has higher solubility. When compared with the counterparts prepared at different temperature, the hollow nanospheres showed excellent optical properties and enhanced photocatalytic acivity which can be attributed to the special hollow structure and the resulting large surface area.