We have studied the surface termination of ZnO(0001¯) films grown on Al 2 O 3 substrates with high epitaxial quality. The structural properties of the ZnO films were investigated by X-ray scattering, revealing a predominant (0001¯)ZnO out-of-plane texture with the [112¯0] ZnO ‖[0001]Al 2 O 3 and [112¯0] ZnO ‖[101¯0]Al 2 O 3 azimuthal orientations for (112¯0)Al 2 O 3 and(0001)Al 2 O 3 substrates, respectively. The surface termination was determined by X-ray photoemission spectroscopy (XPS) via pyridine (C 5 H 5 N) adsorption at the ZnO surface. XPS data recorded at different temperatures after exposure to pyridine revealed that for both orientations of the Al 2 O 3 substrates the deposited ZnO films were terminated by oxygen atoms, i.e. corresponding to a ZnO (0001¯) surface.