Solid solutions of the perovskite structure, (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃with x = 0.1–0.5, were synthesized via the columbite–(wolframite) precursor method. The phase development of calcined powder precursors was analyzed by X-ray diffraction. Phase-pure perovskite of PZN–PZT ceramics was obtained over a wide compositional range. The microstructure and piezoelectric properties were characterrized by means of scanning electron microscopy (SEM), d₃₃ measurements and impedance analysis. It has been found that ultra-high piezoelectric properties were observed in compositions close to a morphotropic phase boundary (MPB). The maximum value of d₃₃ (690 pC/N) and the highest k_p (0.7) were recorded for the composition x = 0.3 located at the boundary between tetragonal and rhombohedral ferroelectric phases. Furthermore, large values of d₃₃ (600 pC/N) and k_p (0.67) were observed at a compositions of x = 0.5, which is the boundary between two ferroelectric rhombohedral phases.