Antimony-doped ZnO layers have been grown by metalorganic vapour-phase epitaxy on sapphire and ZnO substrates at high-temperature (950 °C) and low-pressure conditions (50 torr). Nitrous oxide and diethyl-zinc have been used as oxygen and zinc precursors, respectively. The incorporation of antimony has been obtained from the decomposition of triethylantimony doping molecules added in the gas phase. High Sb concentrations were measured from 1019 to 1021 at/cm−3 using secondary ion mass spectroscopy and depend on the nature and the orientation on the substrate. Low-temperature photoluminescence spectra of Sb-doped layers exhibit donor–acceptor pair transitions at 3.253 eV. Unlike Raman spectra of nitrogen-doped ZnO layers which show several local vibrational modes related to nitrogen incorporation, these modes were found to be absent in the antimony-doped ZnO layers. Transmission electron microscopy suggests that the incorporation of Sb is partly related to dislocations and other structural defects. All together, the characterizations suggest the formation of acceptor dopant–defect complexes, such as SbZn-2VZn. Finally, ZnO:Sb/n-ZnO homojunction diodes have been successfully elaborated on ZnO substrate. The current–voltage characteristics of the device exhibit a rectifying behaviour with a turn-on voltage of 3 V.