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Lead‐free perovskite (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT06) was prepared by conventional ceramic fabrication technique at 1160°C/3h in air atmosphere. The crystal structure, microstructure, dielectric, polarization, piezoelectric properties, and ac conductivity of the sample were studied. X‐ray diffraction data confirmed the formation of a single phase tetragonal unit cell. Williamson‐Hall plot was used to calculate the lattice strain and the apparent particle size. The experimental relative density of BNBT06 was found to be ~96‐97% of the theoretical one with an average grain size ~4 μm. Room temperature dielectric constant and loss factor at 1 kHz were found to be equal to 781 and 0.085, respectively. Longitudinal piezoelectric charge coefficient of the poled sample under 2.5 kV/mm at 80°C in silicone bath was found to be equal to 124 pC/N. Complex impedance and electric modulus spectroscopic analyses …