The growth and characterization of epitaxial Co3O4(111) films grown by oxygen plasma-assisted molecular beam epitaxy on single crystal alpha-Al2O3(0001) is reported. The Co3O4(111) grows single crystalline with the epitaxial relation Co3O4(111)[(1) over bar2 (1) over bar]parallel to alpha-Al2O3(0001)[10 (1) over bar0], as determined from in situ electron diffraction. Film stoichiometry is confirmed by X-ray photoelectron spectroscopy, while ex situ X-ray diffraction measurements show that the Co3O4 films are fully relaxed. Post-growth annealing induces significant modifications in the film morphology, including a sharper Co3O4/alpha-Al2O3 interface and improved surface crystallinity, as shown by X-ray reflectometry, atomic force microscopy and electron diffraction measurements. Despite being polar, the surface of both as-grown and annealed Co3O4(111) films are (1 x 1), which can be explained in terms of a surface inversion in the spinel structure. (C) 2009 Elsevier B.V. All rights reserved.