Perovskite types (1 − x)[PMN–PT(65/35)]–xPZ (with x = 0, 0.1, 0.3, 0.5, 0.7 and 0.9) piezoelectric ceramics were prepared by a modified columbite precursor method. The lattice parameters of the (1 − x)[PMN–PT(65/35)]–xPZ ceramics increase with the addition of larger Zr4+ ion compared to that of other B-site ions. The SEM photographs of all the samples with different PZ content exhibit homogeneous and dense microstructure. The P–E loops indicate the PMN–PT–PZ ternary system has excellent ferroelectric properties. Both d33 and kp dependences in PZ content show similar variation. Introduction of a small amount of PZ content in the PMN–PT(65/35) ceramics enhanced the relaxor behavior, which was confirmed by studying frequency and temperature-dependent dielectric behavior. The increasing values of diffuseness parameter obtained from the fit of a modified Curie–Weiss law established the relaxor nature.