Nd 3+ -substituted lead free 0.94(Na0.5Bi0.5-XNdXTiO3)-0.06BaTiO3 (x=0, 0.01) ceramics were synthesized by using conventional solid state route. The XRD studies revealed the phase purity and existence of the monoclinic (Cc), cubic (Pm3m) along with the minor tetragonal phases confirmed with help of structural refinement. The electrical poling field induces the structural modification to rhombhohedral (R3c), cubic (Pm3m) along with the minor tetragonal phase (P4mm). The dielectric measurements revealed the relaxor behavior. The coercive field drops remarkable and there is slight improvement in the polarization with the substitution of Nd as compared to the pure 0.94(Na0.5Bi0.5TiO3)-0.06BaTiO3. The luminescence occurred from the optically active element Nd 3+ under the influence of the average crystal symmetry of 0.94(Na0.5Bi0.5TiO3)-0.06BaTiO3. The luminescence quenching observed without any shift in position upon the poling supports the observation of higher symmetric structure.