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In the present paper, the gallium modified lead zirconate titanate ceramics with Zr/Ti = 48/52 (near the morphotropic phase boundary, MPB), having a chemical formula Pb0.98Ga0.02(Zr0.48Ti0.52)0.995O3, was synthesized by a mixed-oxide reaction method and sintered. Analysis of phase formation confirmed the co-existence of two phases (tetragonal and monoclinic symmetry) in the system. Microstructural study by scanning electron microscope showed a non-uniform distribution of large grains over the sample surface and presence of a small amount of micro-size pores. Modulus and impedance studies were carried out at various frequencies (1 kHz–1 MHz) and temperatures (300–350 °C) and showed the contributions of grains in capacitive and resistive properties of the material. The resistance and capacitance of the complex impedance plots are contributed by grains as observed from the Nyquist plots. The experimental data obtained from the Nyquist plot were implemented in an equivalent electrical circuit (RQC). The value of grain resistance and capacitance were obtained using fitting steps with precision at all temperatures. It is assumed that increase of dielectric constant at higher temperatures is due to the substitution of Ga+ ions at the Pb-site.