Abstract ZnO films have been grown on GaSb substrates by metallic Zn thermal evaporation and oxidation by annealing in atmospheric conditions. The evaporation times ranged from 20 up to 80 seconds. The oxidation process was carried out at temperatures from 410 °C to 600 °C. The morphology of the surface as well as the luminescence properties have been studied as a function of the growth conditions. The samples were characterized by means of SEM, micro‐Photoluminescence and Cathodoluminescence spectroscopies. The samples present good luminescence emission; the spectra show an intense UV emission with a low intense band in the visible. SbO x phases seem to be formed for some specific growth conditions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)