Recent studies on (0.96)Na0.5Bi0.5TiO3-(0.04)BaTiO3 (NBT-4BT)solid solution reveal the existence of the structural distortion of lower symmetric Cc phase rather than the R3c phase through high resolution X-ray diffraction and neutron diffraction. The Nd-modified NBT-4BT can be thought of a possible candidate for switchable optical properties and has been chosen for present studies. The structural distortion in this solid solution is found to be mixture of two structural phases. The coexistence of Cc along with minor phase reflections of P4mm was confirmed through structural refinement The systematic study of structural, electrical and optical properties on this solid solution has been performed. © 2018 Author(s).