The eco-friendly Na0.5Bi0.5TiO3 (NBT) and its derivatives have been synthesized by conventional solid state route. According to Judd-Ofelt theory, the higher symmetry phase suppresses the electrical and optical properties. Here, the ferroelectric and photoluminescence (PL) properties are influenced by the crystal structure symmetry. In the present work, these properties are optimized with minimal substitution of Nd and Eu at Bi-site in the NBT for introducing PL as an extra functionality without compromising ferroelectric properties. The evolution of photoluminescence in the visible and infrared region has been observed which may be useful in the field of piezochromic based devices. © 2017 Taylor & Francis Group, LLC.