Herein, the synthesis and characterization of zinc (Zn)-modified lead zirconate titanate (PZT) at the morphotropic phase boundary (Zr/Ti = 48/52) (i.e., Pb1−xZnxZr0.48Ti0.52O3 [x = 0.0, 0.03, 0.06, and 0.09]) are reported. The materials are synthesized using a high-temperature solid-state reaction route. Room temperature X-ray structural (Rietveld) analysis confirms the formation of single-phase compounds in tetragonal symmetry. The detailed dielectric studies exhibit that the Curie temperature of the modified PZT is 451, 444, 443, and 442 °C for x = 0.0 (PZT-1), 0.03 (PZT-2), 0.06 (PZT-3), and 0.09 (PZT-4), respectively. The existence of ferroelectric property in the compounds is confirmed through the room temperature electric-field-dependent polarization hysteresis loops. It is found that PZT-1 has the highest dielectric constant ≈4327 (at 1 kHz) at T C as compared with that of other compositions. The frequency–temperature-dependent dielectric and electrical properties demonstrate the contribution of zinc in the conduction mechanism. The observation of grain and grain boundary contributions to the charge carriers, the negative and positive temperature coefficient of resistance (NTCR and PTCR) nature across T C, a controlled (lower) leakage current (≈10−11 to ≈10−13), and the piezoelectric property make the materials useful for several applications. © 2021 Wiley-VCH GmbH