In this article we report the seed-assisted growth of epitaxial ZnO nanorod (NR) arrays on (0001) plane sapphire substrates at low temperatures in aqueous solutions. The self-organized periodic ZnO NR rows with a fairly constant separation were directly grown on bare sapphire surfaces, without the need for any complicated lithography or use of pre-patterned catalysts. The spatial ordering of the ZnO NRs was significantly influenced by the seed growth conditions and by the presence of a self-organized step structure on the annealed sapphire surface. In addition, the effect of the conditions employed to prepare the seeds, including growth parameters and post-growth annealing treatment, on the epitaxial relationship between the ZnO NRs and the sapphire substrate was systematically investigated by X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) observations. Post-growth annealing of the ZnO seeds changed the morphologies and crystallographic alignment of the generated ZnO nanostructures significantly, as a result of the formation of epitaxial spinel ZnAl(2)O(4) interlayers, facilitated by zinc cation diffusion and solid state reactions at high temperature. (C) 2011 Elsevier B.V. All rights reserved.