The structure-property correlation in the lead-free piezoelectric (1 − x)(Na_0.5Bi_0.5)TiO₃-(x)BaTiO₃ has been systematically investigated in detail as a function of composition (0 < x ≤ 0.11), temperature, electric field, and mechanical impact by Raman scattering, ferroelectric, piezoelectric measurement, x-ray, and neutron powder diffraction methods. Although x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc)+rhombohedral (R3c) for the precritical compositions, 0 ≤ x ≤ 0.05, (ii) cubiclike for 0.06 ≤ x ≤ 0.0675, and (iii) morphotropic phase boundary (MPB) like for 0.07 ≤ x < 0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubiclike and theMPB compositions. The cubiclike structure undergoes irreversible phase separation by electric poling as well as by puremechanical impact. This cubiclike phase exhibits relaxor ferroelectricity in its equilibrium state. The short coherence length (~50 A° ) of the out-of-phase octahedral tilts does not allow the normal ferroelectric state to develop below the dipolar freezing temperature, forcing the system to remain in a dipolar glass state at room temperature. Electric poling helps the dipolar glass state to transform to a normal ferroelectric state with a concomitant enhancement in the correlation length of the out-of-phase octahedral tilt.