We report the synthesis and photocatalytic removal of Cr(VI) from water of hierarchical micro/nanostructured Fe2+/TiO2 tubes. The TiO2 tubes fabricated by a facile solvothermal approach show a three-level hierarchical architecture assembled from dense nanosheets nearly vertically standing on the surface of TiO2 microtube. The nanosheets with a thickness of about 20 nm are composed of numerous TiO2 nanocrystals with size in the range of 15-20 nm. Ferrous ions are doped into the hierarchical architecture by a reduction route. The Fe2+/TiO2 catalyst demonstrates an effective removal of Cr(VI) from water under UV light and the removal effectiveness reaches 99.3% at the initial Cr(VI) concentration of 10 mg L-1. The ferrous ion in the catalyst serves not as the photo-electron trap but as an intermedium of a two-step reduction. The TiO2 photoreduces the Fe2+ ions to Fe atoms firstly, then the Fe atoms reduce the Cr(VI) to Cr(III), and the later is removed by adsorption. The hierarchical architecture of the catalyst serves as a reactor for the photocatalytic reaction of Cr(VI) ions and an effective absorbent for the removal of Cr(III) ions. The catalyst can be easily magnetically separated from the wastewater after photocatalytic reaction and recycled after acid treatment. (C) 2011 Elsevier B.V. All rights reserved.