Zinc oxide (ZnO) has drawn much attention due to its excellent optical and electrical properties. In this study, ZnO film was prepared by a high-deposition-rate spatial atomic layer deposition (ALD) and subjected to a post-annealing process to suppress the intrinsic defects and improve the crystallinity and film properties. The results show that the film thickness increases with annealing temperature owing to the increment of oxide layer caused by the suppression of oxygen vacancy defects as indicated by the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) spectra. The film transmittance is seldom influenced by annealing. The refractive index increases with annealing temperature at 300–700 °C, possibly due to higher density and crystallinity of the film. The band gap decreases after annealing, which should be ascribed to the decrease in carrier concentration according to Burstein–Moss model. The carrier concentration decreases with increasing annealing temperature at 300–700 °C since the oxygen vacancy defects are suppressed, then it increases at 800 °C possibly due to the out-diffusion of oxygen atoms from the film. Meanwhile, the carrier mobility increases with temperature due to higher crystallinity and larger crystallite size. The film resistivity increases at 300–700 °C then decreases at 800 °C, which should be ascribed primarily to the variation of carrier concentration.