Talented di-phase ferrite/ferroelectric BaTi.Fe.O@NiFeO (BFT@NFO) in oval nano-morphology was chemically synthesized using controlled sol-gel processes and calcined at 600 °C. The effects of shielding using NiFeO (NFO) nanoparticles on the microstructure, phase transition, thermal, and relative permittivity of BaTi.Fe.O (BTF) nano-perovskite were systematically explored. X-ray diffraction patterns and Full-Prof software exhibited the forming of the BaTiFeO hexagonal phase. TEM and SEM images demonstrated that the coating of BaTi0.Fe.O has been successfully controlled with exquisite nano-oval NiFeO shapes. The NFO shielding can significantly promote the thermal stability and the relative permittivity of BFT@NFO pero-magnetic nanocomposites and lowers the Curie temperature. Thermogravimetric and optical analysis were used to test the thermal stability and estimate the effective optical parameters. Magnetic studies showed a decrease in saturation magnetization of NiFeO NPs compared to their bulk system, which is attributed to surface spin disorder. Herein, characterization and the sensitive electrochemical sensor were constructed for the evaluation of peroxide oxidation detection using the chemically adjusted nano-ovals barium titanate-iron@nickel ferrite nanocomposites. Finally, The BFT@NFO exhibited excellent electrochemical properties which can be ascribed to this compound possessing two electrochemical active components and/or the nano-ovals structure of the particles which can further improve the electrochemistry through the possible oxidation states and the synergistic effect. The result advocates that when the BTF is shielded with NFO nanoparticles the thermal, dielectric, and electrochemical properties of nano-oval BaTiFeO@NiFeO nanocomposites can be synchronously developed. Thus, the production of ultrasensitive electrochemical nano-systems for the determination of hydrogen peroxide is of extensive significance.