A simple self-assembly photochemical reduction method has been proposed to prepare highly photocatalytic TiO2 nanowire/g-C3N4 nanosheet/graphene heterostructures (TiO2/g-C3N4/G). In this hybrid structure, graphene enhances the charge transportation during photocatalytic process, and TiO2 nanowires prevent graphene and g-C3N4 from restacking. Meanwhile, g-C3N4 with a more suitable band gap, extends the adsorption edge of the TiO2/g-C3N4/G composite to visual-region. Benefiting from the positive synergetic effect, 97% of nitrobenzene can be selectively reduced within 4 h by using TiO2/g-C3N4/G as the photocatalyst. The TiO2/g-C3N4/G composite with 3D structure demonstrates a great potential in selective oxidation and reduction of organics for the synthesis of high added-value organic compounds. (C) 2016 Elsevier B.V. All rights reserved.