. Ct, 81.05.Dz, 81.15.Gh CdO thin films have been grown on a-plane (11 2 0), c-plane (0001), r-plane (01 1 2) and m-plane (10 1 0) sapphire substrates by metalorganic vapour-phase epitaxy (MOVPE). The effects of different substrate orientations on the structural properties of the films have been analyzed by means of X-ray diffraction, including θ-2θ scans, pole figures and rocking curves. (111), (001) and (110) orientations are found on a-, r-, and m-sapphire respectively, while films deposited on c-plane exhibit an orientation in which no low-index crystal plane is parallel to the sample surface. The recorded pole figures have allowed determining the epitaxial relationships between films and substrates, as well as the presence or absence of extended defects. The rocking curves indicate that high quality thin films, in terms of tilt and twist, can be obtained on r-, c-and m-plane sapphire, while further improvement is needed over the a-orientation.