We present a comprehensive investigation on the dependence of Nd3+ substitution on various properties in [Na0.5Bi0.5−xNdx]TiO3 (NBNT) for x=0−0.1. The structural analysis of XRD measurements revealed a crossover structural phase transition from monoclinic (Cc) to orthorhombic (Pbnm) for composition s0.04≤x≤0.1. Increase in Nd3+ substitution resulted in larger grain size. Enhanced electrical properties were observed for x=0.01. Dielectric measurements revealed the relaxor behaviour enhances with the content of Nd3+, which is verified with help of bipolar strain loops. The polarization measurements support the evolution of centrosymmetry space group over particular cross over for NBNT with x=0.04. In concomitance with enhanced electrical properties, the luminescence measurements showed the largest emission for x=0.01 for the Nd3+ substituted NBT. The onset of luminescence quenching starts from the substitution of x=0.03 which can be surmised to be due to the effect of centro-symmetric (Pbnm) of orthorhombic structure in addition to the expected concentration quenching effects. The results presented here, establishes the substitution of Nd3+ into the NBT resulted in enhanced electrical and optical properties compared to parent NBT, making these NBNTs promising candidate for multifunctionality applications. © 2017 Elsevier B.V.