An innovative photoelectrode, TiO2/Ti mesh electrode, was prepared by anodisation. In anodisation, 0.5 mol/L H2SO4 was sued as electrolytic solution, the current had been constantly 1A from the beginning of the oxidation until reaching a designed voltage. Results showed that the photocatalytic activity of electrode was better when the designed voltage was 160V. The morphology and the crystalline texture of the TiO2 film on mesh electrode were examined by scanning electronic microscopy and Raman spectroscopy respectively. The examination results indicated that the structure and properties of the film depended on anodisation rate, and the anatase was the dominant component under the controlled experimental conditions. Degradation of Rhodamine B in photocatalytic (PC) and photoelectrocatalytic (PEC) reaction was investigated.