Novel ceramic-polymer nanocomposites have great potential for electrical energy storage applications due to its high energy storage density. In the present work, BNT and PVDF based flexible polymer nanocomposites (BNT-PVDF) with different volume fraction (ϕ = 0, 5, 10, 15) were fabricated by solution casting method. Enhancement in beta phase of PVDF polymer matrix with the volume fraction (ϕ = 5, 10, 15) of BNT has been confirmed by X-ray diffraction (XRD) technique as well as Fourier transform infrared (FTIR) spectroscopy analysis. The enhancement of β phase increases as compared to (α) phases with volume fraction (ϕ) of nanofiller (BNT) in the matrix (PVDF) due to internal stress at the interface as well as structural modification of PVDF matrix. BNT-PVDF nanocomposites (with ϕ=10) showed a high dielectric constant (er ≈ 78) relative to pure PVDF (er ≈ 10) at 100 Hz. In addition to this, it exhibits relaxor type ferroelectric behavior with energy storage efficiency up to 77% for the volume fraction (ϕ) of 10.