Poly(vinylidene fluoride) (PVDF) is a semi-crystalline polymer and the polar beta-phase of PVDF shows superb electroactive properties. In order to enhance the beta-phase of PVDF, extreme low content of BaTiO3 nanoparticles (BT-NPs) coated with polydopamine (Pdop) were incorporated into PVDF matrix by solution casting. The beta-phase of the resulting PVDF nanocomposites film was dramatically increased and the d(33) value reached 34.3 +/- 0.4 pCN(-1). It is found that the Pdop layer could improve the dispersibility and stability of the BT NPs in solution and endow the BT NPs good dispersity in the PVDF matrix. Moreover, the interfacial interaction between PVDF chains and the surface of BT-Pdop nanoparticles (BT-Pdop NPs) were revealed, in which the CF2 groups on PVDF could interact with the electron-rich plane of aromatic ring of Pdop moiety. This interaction, led to the increase of the crystallization activation energy as derived from the DSC nonisothermal crystallization measurement. The alpha-beta crystal transformation, organization of interfacial interactions as well as the prevention of agglomeration of BT-NPs confer the improvement of mechanical and thermal properties of PVDF, such as toughness, tensile strength, elongation at break, and thermal conductivity. 2015 Elsevier Inc. All rights reserved.