Vanadium oxide (VOx) thin films were prepared on unheated glass substrate by pulsed dc reactive magnetron sputtering using different pulse frequency. Field emission scanning electron microscopy (FESEM), x-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry (SE) measurements were made on the deposited VOx films to characterize the microstructure, composition and optical properties, respectively. It was found that under the same discharge power and argon-oxygen atmosphere, with the increase of pulse frequency, the vertical column-like structure in the films will gradually disappear and the ratio of high-valent VOx to low-valent VOx will obviously elevate. Optical parameters of the VOx films have been obtained by fitting the ellipsometric data (Ψ andΔ) using the Tauc-Lorentz dispersion relation and a multilayer model (air/roughness layer/VOx/glass). The results demonstrated that pulse frequency plays a critical role in determining the transmittance, refractive index, extinction coefficient and optical band gap etc. The correlations between the microstructure, composition, optical properties and pulse frequency are also given by our experiment results. And the mechanisms for the evolution of the microstructure, composition and optical properties with pulse frequency have been discussed. Overall, due to the pulse frequency had a great effect not only on the growth characteristics but also on the optical properties of the VOx films, thus through variation of the pulse frequency during deposition which provide a convenient and efficient approach to control and optimize the performances of the VOx films.