The fabrication and evolution of a high performance piezoelectric and ferroelectric material based on poly(vinylidene fluoride)–reduced graphene oxide–barium titanate (PVDF–RGO–BTO(BaTiO₃)) nanocomposites have been investigated. The nanocomposites were obtained by the polymerization of graphene oxide (GO) into the PVDF matrix to achieve an insulator–conductor–insulator sandwich structure, and BTO was then carefully added to the composite. The as-prepared PVDF–RGO–BTO nanocomposite (PRB2) showed a dielectric constant of 98 and relatively low dielectric loss of 0.081 at a frequency of 1 MHz. A very low leakage current density (1.29 × 10⁻⁷ A cm⁻²) was measured at 80 MV m⁻¹, suggesting the high breakdown strength of the PRB2 nanocomposite. Additionally, it exhibited a high energy density of 4.5 J cm⁻³ at an electric field of 50 MV m⁻¹. This high performance piezoelectric–ferroelectric material can be a promising building block for its application in energy harvesting and high frequency capacitors.