We report the efficient photoelectrocatalytic (PEC) reduction of Cr(VI) using TiO2 nanotubes (TNTs) as the photoanode and a large-area Ti mesh as the photocathode. Short-length TNTs (S-TNTs) show much greater PEC activity than either long-length TNTs (L-TNTs) or sol-gel-prepared TiO2 film, due to the fact that the TNT structure is advantageous of trapping light energy over the thin-film structure and the S-TNTs enable the more efficient electron transfer into the substrate than L-TNTs. More importantly, increasing the surface area of the photocathode (Ti mesh) can greatly accelerate the PEC reduction of Cr(VI), presumably due to the increased number of the active reduction sites on the larger-surface Ti mesh. In the PEC reduction of Cr(VI), Cr(V) is identified as a reaction intermediate using the electroparamagnetic resonance technique, whereby the process for the Cr(VI) evolution is proposed. The S-TNTs have been confirmed to be stable over many repetitive cycles of use, indicating their suitability for wide-scale use. (C) 2010 Elsevier B.V. All rights reserved.