Single-crystalline ZnO film with two-dimensional periodic structure was grown on Si(111) substrate by radio-frequency plasma-assisted molecular beam epitaxy. The influence of substrate orientations and growth temperatures was explored for achieving a high-quality ZnO film. It was found that ZnO epilayers grown on Si(111) substrate have better crystalline quality than the one on Si(100). and a higher growth temperature was further confirmed favorable for the attainment of a periodic morphology. The results suggest that our growth method is feasible for the fabrication of ZnO film with periodic structure, which is promising for applications in new photonic devices. (C) 2008 Elsevier B.V. All rights reserved.