©　2018　The　Authors　In　order　to　improve　the　interfacial　compatibility　of　PVDF-based　nanocomposites,　the　BaTiO3　(BT)　nanoparticles　are　coated　successively　using　double-shell　layers　of　hyperbranched　polyamide　polyamide　(HBP)　and　polydopamine　(PDA).　Subsequently,　the　BT　particles　with　an　organic　double-shell　structure　is　compound　to　a　dielectric　poly　(vinylidene　fluoride-chlorotrifluoroethylene)　(P(VDF-CTFE)),　and　the　flexible　0–3P(VDF-CTFE)/BT@HBP@PDA-Ag　nanocomposites　films　with　∼20　μm　in　thickness　are　obtained　using　spin-casting　method.　The　results　of　FTIR,　TEM　and　SEM　indicate　that　the　good　interfacial　compatibility　of　the　composites　favors　the　dispersion　of　coated　BT　particles　in　the　P(VDF-CTFE)　matrix.　Consequently,　the　P(VDF-CTFE)/BT@HBP@PDA-Ag　nanocomposites　film　shows　a　large　dielectric　permittivity　(εr　∼　40)　with　depressed　dielectric　loss　tangent　at　a　low　frequency　of　0.1　Hz.　In　addition,　a　high　electrical　displacement　of　5.6　μC/cm2　and　a　large　discharged　energy　density　of　7.0　J/cm3　are　obtained　in　this　nanocomposite　film　due　to　the　together　contributions　of　ionic　polarization　of　BT　and　the　penetration　effect　of　electrons.　Considering　its　relative　low　dielectric　loss,　the　double-shell　coating　on　the　inorganic　particles　in　the　polymer/ceramic　composite　film　provides　an　effective　way　of　interfacial　fabricating　for　the　high　dielectric　and　energy　storage　performance.