In recent years, VO2 has emerged as a popular candidate among the scientific community across the globe owing to its unique technological and fundamental aspects. VO2 can exist in several polymorphs (such as: A, B, C, D, M1, M2, M3, P, R and T) which offer a broad spectrum of functionalities suitable for numerous potential applications likewise smart windows, switching devices, memory materials, battery materials and so on. Each phase of VO2 has specific physical and chemical properties. The device realization based on specific functionality call for stabilization of good quality single phase VO2 thin films of desired polymorphs. Hence, the control on the growth of different VO2 polymorphs in thin film form is very crucial. Different polymorphs of VO2 can be stabilized by selecting the growth route, growth parameters and type of substrate etc. In this chapter, we present an overview of stabilization of the different phases of VO2 in the thin film form and the identification of these phases mainly by X-ray diffraction and Raman spectroscopy techniques.