ZnO thin films were deposited on Si(111) substrates through a radio frequency (rf) magnetron sputtering system.Then the samples were annealed at different temperatures in air ambience and ammonia ambience respectively. The structure and composition of the ZnO films were studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The morphology of the samples was studied by scanning electron microscopy (SEM). Measured results show that ZnO films with hexagonal wurtzite structure were grown on Si(111) substrates when annealed in the two ambiences. The volatilization process of ZnO in the ammonia ambience at high temperature was discussed and the mechanism of the reaction was analyzed.