ZnO and ZnO:Sb films were deposited using low pressure metal organic chemical vapor deposition on C‐ and R‐oriented sapphire and O‐polar ZnO substrates. Surface morphologies were studied using scanning electron microscopy. Whereas ZnO films grown on C‐sapphire show a rough surface and hexagonal rods, the doped ZnO:Sb layers exhibit a relatively smoother surface, indicating a possible surfactant effect of antimony. The secondary ion mass spectrometry measurements permit to determine the antimony profile in the doped layers. Sb concentrations from 1018 to 1020 at/cm3 were measured, depending on the growth conditions and substrate nature. Photoluminescence spectra exhibit donor–acceptor pair emission at 3.22 eV.