AbstractThe O‐terminated ZnO(000‐1) surface and Mn/ZnO(000‐1) interface have been investigated by synchrotron radiation photoemission spectroscopy (SRPES), low energy electron diffraction (LEED) and X‐ray photoelectron spectroscopy (XPS) systematically. Our results show that ordered O‐polar ZnO(000‐1) surface can be prepared by annealing in an oxygen ambience and this polar surface expresses good chemical stability. At room temperature, metallic Mn film is deposited onto the cleaned ZnO(000‐1)surface and grows in a layer‐by‐layer mode. During the process of Mn film deposition a downward Fermi level movement is observed, and the final resultant Schottky barrier height is 1.07 ± 0.05 eV. High temperature annealing is performed and the interfacial reaction happens evidently. The interfacial chemical reaction and the effect of interfacial dipole layer have been briefly discussed. Copyright © 2007 John Wiley & Sons, Ltd.