Flexible electrostatic capacitors are potentially applicable in modern electrical and electric power systems. In this study, flexible nanocomposites containing newly structured one-dimensional (1D) BaTiO3@Al2O3 nanofibers (BT@ AO NFs) and the ferroelectric polymer poly(vinylidene fluoride) (PVDF) matrix were prepared and systematically studied. The 1D BT@AO NFs, where BaTiO3 nanoparticles (BT NPs) were embedded and homogeneously dispersed into the AO nanofibers, were successfully synthesized via an improved electrospinning technique. The additional AO layer, which has moderating dielectric constant, was introduced between BT NPs and PVDF matrixes. To improve the compatibility and distributional homogeneity of the nanofiller/matrix, dopamine was coated onto the nanofiller. The results show that the energy density due to high dielectric polarization is about 10.58 J cm-3 at 420 MV m-1 and the fast charge.discharge time is 0.126 μs of 3.6 vol % BT@AO-DA NFs/PVDF nanocomposite. A finite element simulation of the electric-field and electric current density distribution revealed that the novel-structured 1D BT@AO-DA NFs significantly improved the dielectric performance of the nanocomposites. The large extractable energy density and high dielectric breakdown strength suggest the potential applications of the BT@AO-DA NFs/PVDF nanocomposite films in electrostatic capacitors and embedded devices. © 2017 American Chemical Society.