Dielectric capacitors with satisfactory energy storage performances are highly demanded. Herein, x vol.% TO@FO@EDA-PVDF nanocomposites combining the novel 1D hybrid TiO2@Fe3O4@ethylenediamine (TO@FO@EDA NWs) as fillers and poly(vinylidene fluoride) (PVDF) as matrix deliver the enhanced energy storage performances. Compared with the TO-, TO@EDA- and TO@FO- filled nanocomposites, TO@FO@EDA filled nanocomposites deliver the highest polarization, breakdown strength and energy storage performances because of the synergistic effects of 1D TO, conductive FO and EDA. As a result, the 2 vol.% TO@FO@EDA-PVDF nanocomposite shows the highest polarization difference (6.92 μC/cm3 at 435 kV/mm), leading to an excellent discharged energy density (13.64 J/cm3), which is 192% higher than that of the pure PVDF (7.11 J/cm3). The primary results might provide a new solution to optimize the energy storage performances of polymer-based nanocomposites.