A novel structure TiO2/Ti film was prepared on a titanium matrix using anodic oxidation technique and applied to degrade Reactive Brilliant Red (RBR) dye in simulative textile effluents. The film was characterized by Field-Emission Scanning Electron Microscope (FE-SEM), Laser Micro-Raman Spectrometer (LMRS), UV-vis spectrophotometer (UVS) and Photoelectrocatalytic (PEC) experiment. The results show that the surface morphology of the film is coral structure, and the crystal structure of the film is anatase. The absorbency of the coral structure TiO2/Ti film is 87-93% in the UV light region, and 77-87% in the visible light region. PEC experiment indicates that the photocurrent density of the coral structure TiO2/Ti film electrode achieves 160 microA/cm(2). The color and Chemical Oxygen Demand (COD) removal efficiencies of RBR achieve 73% and 60% in 1h, respectively. These are 16% and 58% higher than those of nanotube TiO2/Ti film electrode. These were attributed to that these electrodes with different surface morphologies exhibit distinct surface areas and light absorption rate.