The 3D open Bi2MoO6/ZnTiO3 hierarchical heterostructures with Bi2MoO6 ultrathin nanosheets (<10 nm) grown on hexagonal-phase ZnTiO3 nanofibers were fabricated by combining the electrospinning technique and solvothermal method. And, the Bi2MoO6/ZnTiO3 hierarchical heterostructures had remarkable light absorption in the visible region. The photocatalytic studies revealed that the hierarchical heterostructures system exhibited exceptional photocatalytic activity in visible-light degradation of Rhodamine B, which might be attributed to the synergistic system with excellent charge separation characteristics and the unique morphology of Bi2MoO6 nanosheets with the extended absorption in the visible light region. What is more, the 3D open structure supported on nanofibrous candidates possessed large surface areas and excellent recyclability. (C) 2012 Elsevier B.V. All rights reserved.