The relaxor ferroelectric materials can be found in morphotropic phase boundary (MPB) existing between tetragonal and cubic phase. Since the MPB shifts to other phases by adding ceramics composition. [(1 – x)Pb(Mg1/3 Nb2/3)O3–x Pb(Zr0.52Ti0.48)O3] were doped by 0.05Ba(Zn1/3 Nb2/3)O3 when x = 0.4, 0.3, and 0.2 ceramics, which prepared by using a two–step sintering process. The MPB transitions were studied by the use of XRD. The samples, at x = 0.4, were in MPB and then gradually shifted to cubic phase at x = 0.2. The microstructure of samples fracture found that the largest grain size of 4.51 μm for x = 0.2. This study using TEM technique which demonstrated a crystalline morphology with the largest crystal size about 1.293 μm at x = 0.3. These results also revealed that not only the ferroelectric phase shifted to relaxor behavior with decreasing PZT contents in PMN–PZT system but also activated by BZN, which led to the presence of the relaxor behavior.