Vanadium dioxide (VO 2 ) is a compelling candidate for next-generation electronics beyond conventional silicon-based devices due to the exhibition of a sharp metal-insulator transition. In this study, in order to realize functional VO 2 film for flexible electronics, the growth of VO 2 film directly on a transparent and flexible muscovite via van der Waals epitaxy is established. The heteroepitaxy and structural transition of VO 2 films on muscovite are examined by a combination of high-resolution X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The unique metal-insulator transition of VO 2 is further revealed with a change in electrical resistance over 10 3 and a more than 50% variation of optical transmittance. Furthermore, due to the nature of muscovite, the VO 2 /muscovite heterostructure possesses superior flexibility and optical transparence. The approach developed in this study paves an intriguing way to fabricate functional VO 2 film for the applications in flexible electronics.