In this paper, the one-dimensional (1D) Al2O3 nanofibers (Al2O3 NFs), CaCu3Ti4O12 nanofibers (CCTO NFs), and core-shell CaCu3Ti4O12@Al2O3 nanofibers (CCTO@Al2O3 NFs) were prepared via electrospinning technique. The surface modification with dopamine (PDA) was employed for the above three kinds of nanofibers before being filled the PVDF matrix, which can improve their dispersion and compatibility with the matrix. The microstructure, dielectric properties, leakage current density, breakdown strength, and energy storage performance of composites with three kinds of filler, CCTO NFs/PVDF, Al2O3 NFs/PVDF, and CCTO@Al2O3 NFs/PVDF, were systematically investigated. By comparing the three composites, it can be found that energy storage density of CCTO@Al2O3 NFs/PVDF were enhanced compared to that of pure PVDF, which can be attributed to improvement of polarization and electric breakdown strength. The energy density of 8.46 J/cm(3) at 340 kV/mm was obtained for 4 vol % CCTO@Al2O3 NFs/PVDF nanocomposites, which is 230% larger than that of PVDF (3.68 J/cm(3) at 330 kV/mm). This study provides a method for preparing high energy storage PVDF-based composite film which can be used for the next generation of dielectric capacitors.