A single phase 0.94(Na0.5Bi0.5TiO3)-0.06(Ba0.85Ca0.15Ti0.9Zr0.1O3) solid solution (i.e., BCZT-0.06) is prepared using a conventional solid-state sintering route with enhanced piezo and ferroelectric properties as compared to Na0.5Bi0.5TiO3 (NBT). In the context of understanding the origin of enhanced piezoelectric properties in a BCZT-0.06 specimen, electric field driven studies on different length scales, viz., global, local, and electronic structure, are carried out using x-ray/neutron diffraction, Raman scattering, and UV-Vis spectroscopic techniques. An analysis on different length scales of the electric field-driven BCZT-0.06 specimen displays minimum rhombohedral lattice distortion (δr), reduced homogeneous lattice strain (δ), octahedral strain (ζ), and pronounced Ti-cation displacement along the polar [111] direction as compared to parent NBT. The enhanced ferro and piezoelectric responses observed in the BCZT-0.06 specimen have been attributed to the ease of non-180° domain re-orientation, domain switching, and domain wall motion due to reduced strain coupled with a polarization extension mechanism. © 2020 Author(s).