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In this report, we have investigated the effect of BaTiO3 on the preliminary structural analysis, ferroelectric phase transition and electrical properties of (1 − x) P b (F e 0.5 N b 0.5 ) O 3 − x B a T i O 3 (P F N − B T) (x = 0 , 0.025 , 0.05, and 0.1) solid solutions. Conventional solid-state reaction technique is adopted to synthesize P F N − B T solid solution. X-ray diffraction (XRD) analysis is used to study the preliminary structural analysis, which suggests the formation of the single-phase materials. The surface morphology is studied using field emission scanning electron microscope (FESEM). The temperature-dependent dielectric properties display a broad diffuse phase transition from ferroelectric to paraelectric state and the phase transition temperature was found to be decreased with an increase in BT concentrations. Ferroelectric property of the solid solutions is confirmed by the polarization vs. electric field (P–E) loops study at room temperature. Variation of AC conductivity with frequency and temperature is also studied. The addition of BT leads to a decrease in the dielectric loss and phase transition temperature. [ABSTRACT FROM AUTHOR]