In this paper, one of the important, eco-friendly polycrystalline material, (1-x)(Na0.5Bi0.5)TiO3 (NBT)-xBaTiO(3) (BT) of different compositions (x=0.07, 0.06 and 0.05 wt%) around the morphotropic phase boundary (MPB) were synthesized by solid state reaction technique. And the single crystals with 13 x 7 x 7 mm(3), 12 x 12 x 7 mm(3) and 10 x 7 x 4 mm(3) dimensions were grown by self flux method. The morphology, crystal structure and unit-cell parameters have been studied and the monoclinic phase has been identified for 0.07 wt% of BT. Higher BT concentration changes the crystal habit and the mechanism has been studied clearly. Raman spectroscopy at room-temperature confirms the presence of functional groups. The quality of the as grown single crystals was examined by high resolution x-ray diffraction analysis. The dielectric properties of the as grown crystals were investigated in the frequency range of 20 Hz-2 MHz from room temperature to 450 degrees C. The broad dielectric peak and frequency dispersion demonstrates the relaxor behavior of grown crystals. The dielectric constant (epsilon(r)), transition temperature (T-m), and depolarization temperature (Td) of the grown crystals are found to be comparatively good. The diffusive factor (gamma) from Curie-Weiss law confirms the as grown NBT-BT single crystals are relaxor in nature. (C) 2016 Elsevier B.V. All rights reserved.