A photoelectrocatalytic system for removal of ofloxacin and Cu2+ complex was developed. In such a photoelectrocatalytic system, highly ordered titanium dioxide nanotubes served as a highly active photoanode for photoelectrocatalytic degradation of ofloxacin; and titanium plate was used as the cathode, on which Cu2+ ions were electrodeposited. Compared with other treatment methods including photo catalysis, electrochemistry and direct photolysis, photoelectrocatalytic technique exhibited the highest removal efficiency for either ofloxacin or Cu2+. To obtain the optimum photoelectrocatalytic operation conditions, some influencing factors such as current, pH and supporting electrolyte concentration were investigated systematically. The mutual influence analysis indicated that the photoelectrocatalytic removal efficiency of ofloxacin was first promoted by Cu2+ but was then suppressed with prolonging the treatment time; whereas the removal of Cu2+ was always promoted by ofloxacin over the whole photoelectrocatalytic treatment process. Furthermore, the photoelectrocatalytic removal of ofloxacin -Cu2+ was studied by differential pulse voltammetry and high-performance liquid chromatography mass spectrometry. The results indicated that although Cu2+ influenced the removal rate of ofloxacin, it did not change the degradation mechanism of ofloxacin. The formation of an electroactive intermediate product during the photoelectrocatalytic process was clearly observed by voltammetric analysis. Based on intermediate products identified by high-performance liquid chromatography-mass spectrometry, a possible photoelectrocatalytic removal mechanism for ofloxacin -Cu2+ was proposed. (C) 2016 Elsevier B.V. All rights reserved.