Single crystalline, three dimensional (3D) white fungus-like mesoporous Bi2S3 crystals were modified onto the TiO2 nanotube (NT) arrays by pulsed electrodeposition technique which constructs a unique heterojunction photocatalyst bearing large surface area and high adsorbility. The Bi2S3/TiO2 catalyst shows intense absorption in the visible range due to the narrow bandgap of Bi2S3. Under irradiation of solar light, a high efficiency in simultaneously photocatalytic purification of 2,4-dichlorophenoxyacetic acid (2,4-D)/Cr(VI) contaminated water was obtained by employing the Bi2S3/TiO2 NT arrays as photocatalysts. 2,4-D, a stable and toxic aromatic compound, can be effectively decomposed by the hydroxyl radicals initiated by photogenerated holes on the Bi2S3/TiO2 whilst highly poisonous Cr(VI) can be reduced by accepting the electrons and reacting with the byproducts from 2,4-D degradation. 2014 Elsevier B.V. All rights reserved.