An excimer laser assisted metal organic deposition process for the preparation of vanadium dioxide (VO₂) films is described. When a precursor film grown on a silica glass substrate by preheating at 300°C was irradiated with a KrF laser at room temperature in air, the film was crystallized into polycrystalline VO₂ phases. Generally, the preparation of VO₂ films requires strict atmosphere control, but in this process, the polycrystalline VO₂ films were successfully prepared without it. Moreover, it was revealed that crystallization into the VO₂ phases was promoted by a TiO₂ buffer layer placed on the glass substrate. This means that the photochemical reaction induced by the TiO₂ absorbing the laser participates in the crystallization. The electrical resistivity of the film grown on the TiO₂/glass substrate was lowered compared to that of the film grown on the glass substrate due to improvement of the film uniformity. The crystallinity of the obtained film was dependent on the irradiation time. With the improved crystallinity of the film, the resistivity drop through the metal-insulator transition became large.