This report describes the synthesis and characterization of three-dimensional (3D) Nb2O5 Single crystalline nanostructures and three-dimensional Nb2O5/NbS2 cabled networks. The 3D Nb2O5/NbS2 nanostructures are believed to result from the 3D Nb2O5 single crystalline nanostructures which grow along the equivalent crystallographic directions of (1 1 0) in the orthorhombic Nb2O5. These 3D new nanostructures may be potential precursors for creating other complex 31) nanostructures. (C) 2007 Elsevier B.V. All rights reserved.