Zn1−xCdxO(11math0) films have been grown on (01math2) sapphire (r–plane) substrates by metal-organic vapor phase epitaxy. A 800-nm-thick ZnO buffer, deposited prior to the alloy growth, helps to prevent the formation of pure CdO. A maximum uniform Cd incorporation of 8.5 at. % has been determined by Rutherford backscattering spectrometry. Higher Cd contents lead to the coexistence of Zn1−xCdxO alloys of different compositions within the same film. The near band-edge photoluminescence emission shifts gradually to lower energies as Cd is incorporated and reaches 2.93 eV for the highest Cd concentration (8.5 at. %). The lattice deformation, due to Cd incorporation, has been described using a new reference frame in which the lattice distortions are directly related to the a-plane surface structure. Cd introduction does not affect the c lattice parameter but expands the lattice along the two perpendicular directions, [11math0] and [math100], resulting in a quadratic volume increase.