An experimental and theoretical study of the ferroelectric and piezoelectric behavior of PZT doped with barium is presented. Ab initio perturbed ion calculations was carried out. The properties, such as remnant polarization, coercive field and the coupling factor of the PZT at constant sintering temperature was compared with the Zr4+/Ti4+ ions dislocation energy and the lattice interaction energy. An agreement between the experimental and theoretical results, with a decrease of the interaction energy and an inversion of the energy stability from tetragonal to rhombohedral phase was observed.