To realize application in high-capacity capacitors and portable electric devices, large energy density is eagerly desired for polymer-based nanocomposite. The core-shell structured nanofillers with inorganic buffer layer are recently supposed to be promising in improving the dielectric property of polymer nanocomposite. In this work, core-shell structured TO@BT nanoparticles with crystalline TiO2 buffer layer coated on BaTiO3 nanoparticle were fabricated via solution method and heat treatment. The thickness of the TO buffer layer can be tailored by modulating the additive amount of the titanate coupling agent in preparation process, and the apparent dielectric properties of nanocomposite are much related to the thickness of the TO layer. The relatively thin TO layer prefer to generate high polarization to increase dielectric constant while the relatively thick TO layer would rather to homogenize field to maintain breakdown strength. Simulation of electric field distribution in the interfacial region reveals the improving effect of the TO buffer layer on the dielectric properties of nanocomposite which accords with the experimental results well. The optimized nanoparticle TO@BT-2 with a mean thickness of 3-5 nm buffer layer of TO is effective in increasing both the epsilon and E-b in the PVDF composite film. The maximal discharged energy density of 8.78 J/cm(3) with high energy efficiency above 0.6 is obtained in TO@BT-2/PVDF nanocomposite with 2.5 vol% loading close to the breakdown strength of 380 kV/mm. The present study demonstrates the approach to optimize the structure of core-shell nanoparticles by modulating buffer layer and provides a new way to further enlarge energy density in polymer nanocomposite. (C) 2018 Elsevier B.V. All rights reserved.