In this Letter a detailed study of the electric field gradient (EFG) across the Pr(1-x)Ca(x)MnO(3) phase diagram and its temperature dependence is given. Clearly, distinct EFG behavior for samples outside or inside the charge order (CO) region are observed. The EFG temperature dependence evidences a new phase transition occurring over the broad CO region of the phase diagram. This transition is discontinuous and occurs at temperatures between the charge ordering and the Néel temperatures. The prominent features observed in the EFG are associated with polar atomic vibrations which eventually lead to a spontaneous local electric polarization below CO transition.