Polymer nanocomposites (PNC) showing improved physical properties are emerging as novel functional materials because of their adaptable physical properties for technological applications. We synthesized a new PNC system composed of an insulating ferroelectric poly-vinylidene fluoride (PVDF) host and a high dielectric semiconducting Na_xTi_yNi_1−x−yO (Na and Ti co-doped NiO with x = 0.05, 0.15 and y = 0.02) oxide of variable particle sizes (∼0.5–0.6 μm to ∼80–90 nm) as filler. The PNC system exhibited excellent ferroelectric behavior as well as tensile strength with a low percolation threshold (f_c). The observed large enhancement of room temperature effective dielectric permittivity (ε_eff ∼ 600–750 about 60–75 times that of host PVDF matrix) along with a very low dielectric loss of ≤0.18 at 1 kHz, high dielectric breakdown voltage (>140 kV mm⁻¹) and saturation polarization (∼10 μC cm⁻²) near f_c distinguished these PNC films as suitable candidates for capacitor applications in devices.