Herein, we present comprehensive investigations of the optical and electrical properties of Nd3+ substitution in sodium bismuth titanate ceramics (NBNT) with varying Nd3+ concentration. The room temperature photoluminescence (PL) emission for both unpoled and poled samples is observed to be a maximum for an Nd3+ substitution of 1 mol%. Upon poling, the PL intensity is observed to be quenched, consistent with the obtained XRD data, indicating an electric-field induced structural ordering towards higher symmetry, confirmed with the help of structural refinement. The evaluated ferroelectric to relaxor and antiferroelectric relaxor T(F-R) was observed clearly from the poled dielectric-loss curve for the 1 mol% of Nd3+ substitution. Furthermore, the optimized NBNT exhibited a lower Ec and a higher off-resonance figure of merit (FOMoff) for energy harvesting by 12% and 30%, respectively, in comparison with un-doped NBT. © The Royal Society of Chemistry 2018.