Herein we present the successful synthesis of aligned arrays of single-crystalline, 6-fold-symmetrical, hierarchical ZnO nanostructures via a two-step vapor-phase transport method. The X-ray diffraction and transmission electron microscopy results illustrate that the backbones of the as-grown product have excellent orientation along the [001] direction, and the branches epitaxially grow on the backbone along the AE100ae direction. At room temperature, the 6-fold-symmetrical hierarchical ZnO nanostructure arrays exhibit a very strong green luminescence centered at 515 nm. The field emission measurements show that they have a turn-on field of 5.6 V/μm and field-enhancement factor of 1351, which indicate their potential application in field emission nanodevices.Since the discovery of carbon nanotubes, 1 enormous efforts have been devoted to researching one-dimensional (1D) nanostructures due to their exciting physical properties and wide applications in electronic, optoelectronic, and electrochemical nanodevices. [2][3][4][5][6][7][8] Recently, the self-assembly of 1D nanostructures into hierarchical nanoarchitectures as well as nanoheterostructures has become the focus of intensive attention because they may exhibit some novel properties resulting from their unique multidimensional shape and the combination of both micrometer-scale and nanometer-scale building blocks. 9-19 Furthermore, they can be used as building units in nanodevices, which is crucial for the development of future nanodevices and nanotechnology. Up to now, the design and synthesis of hierarchical nanostructures with a controlled crystallographic direction and assembling them into arrays remain one of the main challenges to realize functional nanodevices.As one of the most important multifunctional semiconductors, ZnO with a wide band gap energy of 3.37 eV and a large exciton binding energy of 60 meV at room temperature has a wide range of applications in electronic, optoelectronic, electrochemical, and electromechanical devices, such as ultraviolet (UV) lasers, 6,8 light-emitting diodes, 20 field emission devices, 21 solar cells, 22 and piezo-nanogenerators. 23 In the past few years, hierarchical ZnO micro-and nanostructures with different morphologies were synthesized via gas-phase and solution-phase approaches. 10,[24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] Nevertheless, how to assemble the as-prepared hierarchical ZnO nanostructures into arrays with excellent orientation has remained a challenge. In this study, we report the successful fabrication of aligned arrays of hierarchical ZnO nanostructures via a two-step vapor-phase transport method. The as-synthesized product has essential features of nanoscaled, 6-fold-symmetrical hierarchy and single crystallinity. More important, the backbones of the product have excellent orientation along the [001] direction, and the branches epitaxially grow on the backbone along the AE100ae direction. At room temperature, the photoluminescence (PL) results show that the 6-fold-symmetri...