Hierarchical honeycomb anatase TiO2 with (100) facet was synthesized by using a facile hydrothermal method. The product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and UV-Vis diffused reflectance spectroscopy (DRS), respectively. The photocatalytic activity of the product was investigated on the degradation of Rhodamine B (RhB). It was found that the absorptive wavelength edge of the product was 400 nm, which shifted to the red light compared to the ordinary anatase TiO2. The anatase TiO2 honeycomb, which was comprised from curling nanoflake, exhibited excellent photocatalytic performance. Under the simulate sunlight irradiation for 20 minutes, the degradation rate of RhB nearly reached 80%. And after being irradiated for 40 minutes, the degradation rate reached 99.0%, close to decomposing completely. It indicated that the photocatalytical activity of honeycomb anatase TiO2 was better compared to P25 and it would be widely used in industrial application and environmental remediation.