Wormhole-shaped F-doped TiO2/Ti photoelectrodes were prepared by microarc oxidation method in NaF solution. The morphology and structure of the photoelectrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF). It was found that F-doped TiO2/Ti photoelectrodes were porous and composed of anatase TiO2. The photocatalytic properties of F-doped TiO2/Ti photoelectrodes were investigated by photodiscoloration rate of Rhodamine B(Rh.B) under different conditions. All results showed that the photoelectrodes prepared at voltage of 160V, NaF concentration of 0.01mol/L and oxidation time of 10min have optimal photocatalytic performance. Rh.B was almost completely removed by F-doped TiO2/Ti photoelectrodes after 120min under the illumination of artificial visible light.