TiO2 nanotube arrays sensitized by copper nanoparticles (TiO2 NTs/Cu) exhibited highly efficient photoelectrocatalytic removal of RhB and Cr(VI). Vertically grown anatase TiO2 NTs on Ti substrates were prepared by electrochemical anodization followed by calcinations. Subsequently, Cu nanoparticles with uniform spherical structures and size distributions were deposited on TiO2 nanotubes by a modified hydrothermal reaction. By exploiting TiO2 NTs/Cu as both photoelectrodes and photocatalysts, high photocurrent density and photoelectrocatalytic removal efficiencies of RhB and Cr(VI) were achieved under solar light irradiation. The enhancement on the photoelectrochemical performance was explained by the optoelectronic coupling between Cu nanoparticles and TiO2 NTs, which accelerated the transfer rate of electrons, and subsequently decreased the electron/hole pair recombination. (C) 2016 Elsevier B.V. All rights reserved.