A new organic sol-gel spin-coating method was adopted to prepare the vanadium oxide (VOx) thin films. In this method, the sol-gel adopted was formed from the dispersion consisted of different proportions of V2O5 powder, benzyl alcohol and iso-butanol. Spin-coating technology and thermal-resistance properties of the VOx thin films were systematically investigated. In this method, V5+ in the solution was reduced to form the V4+ isobutanol complex. Compared with conventional inorganic sol-gel process, little hydrolysis happened and little precipitation was produced, and temperature for the post-heating treatment is relatively low. Compared with conventional organic sol-gel process, the raw materials used in this method have relatively low prices.