Highly crystalline CuSe hierarchical nanostructures made of nanosheets have been successfully synthesized on the surface of TiO2 nanotube arrays (NTs) pre-loaded with Cu2O nanowires using a photo-assisted chemical bath deposition. The pre-synthesized Cu2O nanowires served as copper precursor and nucleation centers for the crystal growth, resulting in the rapid formation of CuSe crystals at low temperature. This novel material held the advantages of both p-n junction and hierarchical nanostructures which provided high specific surface areas, thus facilitating the transfer of the electrons and inhibiting the recombination of the photogenerated hole-electron pairs, which were demonstrated by photoelectrochemistry measurements. Meanwhile, UV-vis diffuse reflectance spectra (DRS) showed the modified TiO2 significantly enhanced the absorption in the visible light region. X-ray diffractometer (XRD) and high resolution transmission electron microscopy (HRTEM) were employed to demonstrate that the resulting CuSe was single crystalline. A possible mechanism was proposed to explain the formation of rosalike architecture CuSe at low temperature. In addition, this novel material exhibited remarkable photocatalytic performance on the degradation of anthracene-9-carboxylic acid (ACA). (C) 2012 Elsevier Ltd. All rights reserved.