In this paper, the 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 nanofibers (BZT-BCT NFs) with high aspect ratio were synthesized by electrospinning technique, and the PVDF-based composites filled with the BT NPs or BZT-BCT NFs were fabricated. Obviously, compared to the BT NPs/PVDF composite, the dielectric properties of BZT-BCT NFs/PVDF composites are improved at given volume fraction. The electric modulus formalism indicated that the BZT-BCT NFs could effectively enhance the interfacial polarization of the BZT-BCT NFs/PVDF composites than that of the BT NPs/PVDF composite. In addition, the BZT-BCT NFs with large aspect ratio can make the composites polarize at a higher field strength, thus the composites obtain higher polarization strength. The energy density of 3 vol% BZT-BCT NFs/PVDF composite is 3.08 J/cm3 at 240 kV/mm, which is 2.01 times higher enhancement than the BT NPs/PVDF composite (1.53 J/cm3 at 180 kV/mm). These results also provide a simple but effective method to achieve the materials with high capacitance for energy storage. Keywords: Powders, Nanocomposites, Interfaces, Dielectric properties, Energy storage density