The method of Ti/TiO2 photoelectrode prepared by using laser calcination method instead of oven calcination process was introduced. The prepared TiO2 film was observed with AFM and XRD. Photoelectrocatalytic degradation of rhodamine B (RB) using this electrode was investigated, and anodic potential and pH were optimized. The laser power applied in this electrode preparation was also discussed, and it indicated that TiO2 particle prepared with high laser power was crystallized adequately and the photoelectrocatalytic ability was satisfactory. RB degradation was investigated under different conditions, and it showed that photoelectrocatalytic degradation could achieve efficient and complete mineralization of organic pollutant. The photoelectrocatalytic oxidation using the Ti/TiO2 electrode calcinated by laser was compared with that of the electrode calcinated by furnace, and it showed that the reaction rate of RB degradation using the electrode by laser was faster than that by furnace. Additionally, electrochemical impedance spectroscopy (EIS) was performed at the two different photoelectrodes, which verified the higher photocatalytic activity of the laser-treated electrode further. (c) 2006 Elsevier Ltd. All rights reserved.