Pyrochlore-free lead zirconate titanate – lead zinc niobate ceramics have been systematically investigated in the as-sintered condition as well as after annealing. The ceramics were characterized by dielectric spectroscopy and Sawyer–Tower polarization (P–E) measurements. The powders of Pb[(Zr_1/2Ti_1/2)_(1−x)–(Zn_1/3Nb_2/3)_x]O₃, where x = 0.1, 0.3 and 0.5 were prepared using the columbite–(wolframite) precursor method. The general trend seems to indicate that the annealed samples become more normal-ferroelectric-like behavior as opposed to the relaxor-ferroelectric-like behavior observed in the as-sintered state. The as-sintered 0.9PZT–0.1PZN ceramic exhibited weak relaxor-ferroelectric behavior, with a relatively low dielectric constant maximum of 14,000 measured at 1 kHz. Annealing resulted in a transition to normal-ferroelectric-like behavior, a shift in the dielectric maximum temperature from 360 °C to 350 °C, and a dramatic increase in the dielectric constant at 1 kHz to a maximum value of 35,000 for the longer anneal. After thermal annealing at 900 °C for one week a strong enhancement of remanent polarization (P_r) was observed.