Comprehensive investigations on the effect of mechanical and chemical processing techniques on structural, electrical and photocatalytic properties of single phase lead-free Na0.5Bi0.5TiO3 (NBT)and their correlations are presented here. NBT is synthesized using solid-state (NBT-SSR), sol-gel (NBT-SG), combustion (NBT-C)and hydrothermal (NBT-H)techniques. The structural analysis confirmed the rhombohedral (R3c)phase stabilization in the solid-state synthesized sample whereas a minor monoclinic (Cc)phase coexisted with R3c phase in chemically synthesized samples. The robust relaxor feature along with slanted ferroelectric hysteresis loop (for energy storage)was observed in hydrothermally synthesized NBT samples (NBT-H). The ferroelectric hysteresis loop gradually became slanted due to the multi-domain to the mono-domain transformation that eased the domain reversal and switching which was observed through lower coercive field (Ec)values. NBT ceramics synthesized using combustion technique (NBT-C)appeared to be the best target catalyst to probe the influence of ferroelectricity on the decolorization of Rhodamine B dye under simulated visible light. © 2019 Elsevier B.V.