In this study, we report the synthesis, microstructural and electrical characterization of lead-free (1-x)Na1/2B1/2TiO 3-xBaTiO3 (NBT-BT) ceramics with x = 0.05, 0.06, 0.07, 0.08, 0.09. NBT-BT ceramics were synthesized using conventional solid state reaction method. The piezoelectric response was optimized by synthesizing the compositions around morphotropic phase boundary (MPB). All the samples were characterized by XRD for structural information, scanning electron microscopy for microstructure and elemental analysis, and electrical measurements for dielectric and piezoelectric constants. The density was measured using Archimedes principle and was found to be more than 96% of theoretical density for all the specimens. The values of permittivity (εT 33/ε0) and longitudinal piezoelectric constant (d33) for x = 0.07 were found to be 1027 and 160 pC/N, respectively along with radial mode electromechanical coupling factor of kp ∼ 0.22. For x = 0.08, the values of d33 and kp were found to be 151 pC/N and 0.35 respectively. The piezoelectric response measured in present study was found to exhibit systematic variation with composition and exhibited high magnitude as compared to reported values in literature. Further, this study provides deterministic information on calcination and sintering temperature of NBT - BT ceramics close to the morphotropic phase boundary (MPB).