In this study, TiO2 nano-particles decorated TiO2 nano-tubes arrays (TiO2 NPs/TiO2 NTAs) photoelectrodes have been successfully prepared through anodization, combined with ultrasonic strategy, followed by annealing post-treatment. The morphology and structure of the as-prepared TiO2 NPs/TiO2 NTAs photoelectrodes were characterized by scanning electrons microscopy (SEM), N-2 adsorption/desorption isotherms, X-ray diffraction (XRD) and UV-visible light diffuse reflection spectroscopy (DRS). In addition, the generation of hydroxyl radicals ((OH)-O-center dot) was detected by a photoluminescence (PL) spectra using terephthalic acid (TA) as a probe molecule. Furthermore, the photoelectrochemical (PECH) properties of TiO2 NPs/TiO2 NTAs photoanode were investigated through transient open circuit potential (OCP), photocurrent response (PCR) and electrochemical impedance spectroscopy (EIS). It was found that TiO2 NPs/TiO2 NTAs photoelectrode exhibited a distinct decrease of OCP of -0.219 mV cm(-2) and PCR of 0.049 mA cm(-2), while a significantly enhanced photoelectrocatalytic (PEC) efficiency of 63.6% (0.4V vs. SCE) for the degradation of diclofenac. Moreover, the enhanced PEC mechanism of TiO2 NPs/TiO2 NTAs photoanode was proposed. The high PEC performance could be attributed to the decoration of TiO2 NPs, which could improve the mobility and separation efficiency of photoinduced charge carriers under external potential. (C) 2013 Elsevier Ltd. All rights reserved.