Hierarchical tree-, mushroom- and cockscomb-like ZnO arrays with increasing branching order and complexities have been grown in situ on cheap zinc plates by a simple hydrothermal oxidation approach. Their morphology, crystal structure and orientation relationship are characterized by powder X-ray diffraction, scanning electron microscopy (SEM) and cross-sectional high-resolution transmission electron microscopy (HRTEM). The wurtzite ZnO arrays, growing mainly in the [0001] direction, show a special orientation relationship between the stem and the branch as well as a novel stem-branch boundary which might be attributed to the least mismatch between [symbol: see text] and (0002) lattice planes. The co-solvent ethylenediamine (en) was used to control the morphology and complexing of these complex ZnO nanostructures. Correspondingly, the physical properties of ZnO nanostructure assembly arrays were tuned and a stronger UV emission was observed with negligible emissions in the visible range, indicating the highly crystalline features of the complex ZnO micro-/nanostructured materials.