Pure and Co-doped zinc oxide nanomaterials were prepared by a simple low temperature synthesis and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution-transmission electron microscopy (HR-TEM), diffused reflectance spectroscopy (DRS) and electron paramagnetic resonance (EPR) techniques. The results showed the formation of nanobushes that consists of several nanowires for pure ZnO and the nanorods formed by self-aggregation for Co-doped ZnO. The presence of Co2+ ions replacing some of the Zn2+ in the ZnO lattice was confirmed by EPR and DRS studies. The mechanism for the formation of self-aggregated and self-aligned ZnO rods after the incorporation of cobalt in the lattice by the building block units is discussed in this study. Morphological studies were carried out using SEM and HR-TEM, which supports the validity of the proposed mechanism for the formation of ZnO nanobushes and Co-doped ZnO nanorods. The synthesized nanomaterials were found to have good optoelectronic properties. © 2010 Elsevier Ltd. All rights reserved.