We demonstrated in this paper that polypyrrole encapsulated in highly ordered TiO2 nanotubes array (PPy/TiO2 NTs) electrode could be obtained via two steps: (1) electrosynthesis of TiO2 nanotube array in HF solution by anodization method; (2) followed by electropolymerization of pyrrole encapsulated in the TiO2 nanotubes array. The morphological characteristics and structures of PPy/TiO2 NTs electrode were examined by field-emission scanning electron microscopy, X-ray diffraction, and energy dispersive X-ray spectroscopy. The photoclectrochemical properties were studied in a three-electrode cell with 0.5 M Na2SO4 solution as supporting electrolyte. The photocurrent was dramatically enhanced on the PPy/TiO2 NTs electrode, comparing with that on bare TiO2 NTs electrode. A photocurrent density of 1.52 mA cm(-2) and the incident photon to electron conversion efficiency of 73.21% were obtained under an UV illumination of 10 mW cm(-2). (c) 2008 Elsevier B.V. All rights reserved.