This article describes a novel and simple route to preparing VO(2) thermochromic films by using a VOCl(2) solution with poly(vinylpyrrolidone) (PVP). X-ray diffraction and Raman spectra showed that the VO(2) films deposited with PVP consisted of a nearly pure monoclinic/rutile (M/R) phase. Conversely, films prepared without PVP contained obviously impure crystalline phases. The as-prepared films with PVP showed excellent optical properties compared to those prepared by common gas-phase methods: an integral visible transmittance of 54.5% and an IR reduction (change in transmittance) of 41.5% at 2000 nm. The phase-transition temperatures were adjusted from 69 to 54 degrees C by tungsten doping. Equipment analyses revealed that PVP plays two roles in the film formation. First, it fundamentally acts as a film-forming promoter to improve physical gelation via interactions among oppositely charged carbonyl groups and amine groups of the polymer. Second, the negatively charged carbonyl groups can interact with VO(2+) to form a uniform mixed-gel film after solvent evaporation. Thus, the addition of PVP can stabilize the solution and improve the as-prepared film quality and phase purity. The current study suggests that the process has promise in applications of smart windows.