Angle-resolved photoelectron spectroscopy and low-energy electron diffraction measurements have been carried out to characterize the Cu oxide overlayer formed on the Zn-terminated ZnO(0001) surface. Deposition of Cu and subsequent oxidation lead to Cu₂O with (111) orientation. The Cu₂O(111) lattice structure is expanded so as to realize the epitaxial relationship to the underlying ZnO surface. The valence-band maximum of the Cu₂O overlayer is found to be shifted to the lower-binding-energy side by ∼ 0.4 eV in comparison with that of bulk Cu₂O, suggesting a stronger p-character of the overlayer than the bulk material. [DOI: 10.1380/ejssnt.2008.226]