The ceramic (Pb_1-XBa_X)ZrO₃ composition, hereafter abbreviated PBZ-x, is a ceramic solid solution with perovskite structure. The effect on the antiferro-ferro-paraelectric phase transitions sequence caused by Barium substitution in Pb-sublattice is Raman spectroscopically evidenced and discussed. Furthermore, the basic features of the composition-temperature phase diagram of PBZ-x (x ≤0.5) solid solutions were established.