VO2 thin films have been studied for their semiconductor-metal reversible transition from the monoclinic to the rutile structure, where the electrical and optical properties undergo a drastic change by increasing the temperature or by applying a voltage. VO2 film is becoming a promising material for optical switch, optical storage, optical modulator, smart window, and micro-bolometer. The preparation procedures of the FTO/VO2/FTO structure in detail are as follows: First, the F-doped SnO2 conductive glass (FTO) substrates are cleaned sequentially in acetone, ethanol, and deionized water for 10 min using an ultrasonic cleaning equipment at a frequency of 20 kHz. When the FTO substrates was cleaned, they are dried with nitrogen. Second, the dried FTO substrates are placed in the chamber of a DC magnetron sputtering system equipped with a high-purity metal target of V (99.9%). After argon (99.999%) of 80 sccm flux was discharged with the current of 2 A and the voltage of 400 V for 2 min, the vanadium films are deposited on the FTO substrates. Third, the prepared vanadium films are annealed for different annealing time in an atmosphere composed of different proportions of nitrogen-oxygen. Then another layer thickness of 350 nm of FTO conductive film is deposited on the VO2 thin film by using the plasma enhanced chemical vapor deposition method. Finally, different sizes of the FTO/VO2/FTO structure are prepared by using photolithography and chemical etching processes. The effect of different annealing time and different proportions of nitrogen-oxygen atmosphere on the VO2 thin films has been studied. X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and spectrophotometer are then used to test and analyze the crystal structure, surface morphology, surface roughness, the relative content of the surface elements, and transmittance of the VO2/FTO composite films. Results show that a relatively single component VO2 thin film can be obtained under the optimum condition. The current abrupt change can be seen at the threshold voltage when the FTO/VO2/FTO structure is applied to voltage on both the transparent conductive films of the VO2 thin film. The threshold voltage is 1.7 V when the contact area is 3 mm×mm, and the threshold voltage increases as the contact area increases. When the contact area is 6 mm × 6 mm, the threshold voltage of the thin film phase transition is 4.3 V; when the contact area is 8 mm × 8 mm, the threshold voltage of the thin film phase transition is 9.3 V. Compared with the no voltage situation, the infrared transmittance difference of the FTO/VO2/FTO structure under the effect of voltage is up to 28% before and after the transition. The structure remains stable with a strong electrochromic capacity when it is applied with voltage repeatedly. This brings about many new opportunities for optoelectronic devices and industrial production.