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The growth of high quality ZnO films is highly desirable due to the promising applications of ZnO in optoelectronics. In this paper, ZnO films were grown on the MgO(111) substrates via the growth technique of molecularbeam epitaxy and their structural and optoelectronic properties were characterized. In particular, the influence of growth condition on the film qualify was investigated. The results show that, inducing a low temperature ZnO buffer layer before the high temperature growth of ZnO films will help to improve the film quality. In situ reflection high-energy electron diffraction (RHEED) and ex situ X-ray Diffraction (XRD) measurements indicate that the ZnO film and the MgO substrate follow the epitaxial relationship: ZnO[1-210]//MgO[1-10] and ZnO[1-100]//MgO[11-2]. Transmission Spectra show the characteristic optical bandgap of ZnO.