We report on the formation of ZnO/carbon nanotubes heterostructures achieved by means of a thermal evaporation method. Scanning electron microscopy revealed that the main building block of the observed morphologies was the nanorod whose self-assembling resulted in various structures such as polypods and nano-hedgehogs, depending on various factors as well as the location of the ZnO-CNT junction. X-ray diffraction and photo luminescence spectroscopy were used to study the structure and optical properties of obtained nanostructures. Semi-empirical molecular orbital calculations gave evidence for the nature of the binding between ZnO and CNTs. (c) 2007 Elsevier B.V. All rights reserved.