Epitaxial ZnO thin films have been synthesized directly on Si(1 1 1) substrates by pulsed laser deposition (PLD) in vacuum. The reflection high-energy electron diffraction (RHEED) indicates that streaky patterns can be clearly observed from the ZnO epilayers prepared at 600 and 650 degrees C, revealing a two-dimensional (213) growth mode. While the ZnO thin film deposited in oxygen ambient shows ring RHEED pattern. There is a compressive in-plane stress existing in the ZnO epitaxial film, but a tensile one in the polycrystalline film. Compared with the ZnO epilayer, the ZnO polycrystalline film shows more intense ultraviolet emission (UVE) with a small full width at half maximum (FWHM) of 89 meV. It is suggested that the atomically flat epilayers may be powerfully used as transitive stratums to grow high-quality ZnO films suitable for the fabrication of optoelectronic devices. (C) 2007 Elsevier B.V. All rights reserved.