Single orientation ZnO (00.2) films were deposited by means of high temperature high vacuum reactive magnetron sputtering onto Al2O3 (0001) and GaN (0001) substrates. In order to obtain films of high crystalline quality a novel approach to ZnO sputter deposition was employed, adapting the practice used in MBE technology, of using a MgO buffer layer deposited on sapphire at a high-temperature followed by a ZnO nucleation layer deposited at low temperature. ZnO films were also grown on epitaxial GaN/Al2O3 substrates where the GaN layer was treated as the buffer layer. Following the deposition, all samples were annealed ex-situ in an O2 flow at 800°C. The obtained ZnO films have a lattice constant c equal to 5.2036 Å and 5.214 Å for the films deposited on Al2O3 and GaN substrates, respectively. Secondary ion mass spectroscopy depth profiles, scanning and transmission electron microscopy cross sectional images and atomic force microscope were used to characterize the structural properties of the films. Electrical properties were assessed using Hall effect measurement. Photoluminescence spectra were also taken.