The optical and structural properties of high-quality single-crystal epitaxial MgZnO films deposited by pulsed-laser deposition were studied. In films with up to ∼36 at. % Mg incorporation, we have observed intense ultraviolet band edge photoluminescence at room temperature and 77 K. The highly efficient photoluminescence is indicative of the excitonic nature of the material. Transmission spectroscopy was used to show that the excitonic structure of the alloys was clearly visible at room temperature. High-resolution transmission electron microscopy, x-ray diffraction, and Rutherford backscattering spectroscopy/ion channeling were used to verify the epitaxial single-crystal quality of the films and characterize the defect content. Post-deposition annealing in oxygen was found to reduce the number of defects and to improve the optical properties of the films. These results indicate that MgZnO alloys have potential applications in a variety of optoelectronic devices.