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In order to explore a solution for the application of molecular switchable dielectric material in the form of thin film,a layered structure of grain-oriented flexible composite film is designed and prepared by incorporating polar and switchable dielectric single-protonated 1,4-diazabicyclo[2.2.2]octane perrhenate(DabcoHReO4)into β-phase dominated PVDF matrix.Utilizing the induced orientation effect at the interface between β-phase PVDF and polar guest,DabcoHReO4 could be orientedly arranged in composite film.Our study found that β-phase dominated PVDF composite film with 40%of salt content could exhibit larger dielectric change between high and low dielectric states than that of pure DabcoHReO4 at phase transition temperature.We postulated that the enhanced switchable dielectric property should be attributed to the induced orientation of β-phase dominated PVDF and dielectric confinement effect.This study is likely to pave the way toward practical application in devices for molecular switchable materials.