This study presents an electrosynthetic methodology to obtain hierarchically structured ZnO electrodes with improved surface area, by exploiting gold nanowires ensembles (3D-NEEs) as the growing substrate. By this way, semiconductor electrodes organized in the shape of fir-like branches are obtained. Branched nanofibres are characterized by electron microscopy and electron backscatter diffraction (EBSD), the latter technique allowing the determination of the crystalline habit of individual nanostructures. The hierarchical branched nanowires show enhanced performances with respect to water photooxidation in comparison with already known nanostructured materials such as 1D-ZnO nanowires. (C) 2012 Elsevier Ltd. All rights reserved.