Integration of ZnO with the well-developed GaAs technology presents several aspects that need to be previously analyzed and considered. The large lattice mismatch between ZnO and GaAs and its different crystallographic structure lead to many structural defects. In addition, their potential chemical reactivity is another source of complexity and an academic challenge. Recently some interesting contributions on this subject have been carried out by Liu and co-workers. As an additional step to the knowledge of the ZnO/GaAs heterostructure, we have deepened on the study of the morphology and orientation of ZnO thin films grown by atmospheric pressure metal-organic chemical vapour deposition (AP-MOCVD) on GaAs(100) and GaAs(111)A substrates with and without a Zn buffer pre-deposition on them. The analysis has been made as a function of growth temperature and precursors ratio. Structural, morphological and compositional characterizations have been made by X-ray diffraction (XRD), high-resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM), energy dispersive X-ray microanalysis (EDX) and X-ray photoemission spectroscopy (XPS). ZnO layers present an out-of-plane (0001) preferred orientation, while the in-plane orientation has a random distribution. The layers are constituted by large tilted columnar grains with a top angle of around 55 degrees indicating that the planes which constitute the conic heads are the {10 (1) over bar1} ones. ZnO films grown after a previous Zn deposition exhibit a less compact morphology. In some cases and depending on growth conditions, interfacial processes with crystallization of extrinsic phases have been observed by XRD, revealing the presence of a body centred tetragonal phase of Zn3As2. in order to get an insight into these interfacial effects, EDX on cross-sectional views of the interface has been carried out. Strain measurements indicate a tensile nature of the biaxial stress, which is reduced by a factor two when the Zn buffer is used. (C) 2009 Elsevier B.V. All rights reserved.