Single crystals of (Na1/2Bi1/2)TiO3-based compositions are of interest for actuator applications. In this work, single crystals of nominal composition (Na1/2Bi1/2)TiO3 (NBT) and 0.92(Na1/2Bi1/2)TiO3–0.08KNbO3 (NBT-KN) are grown by the self-flux method and their structure and electrical properties characterized. X-ray diffraction and transmission electron microscopy show that both the NBT and NBT-KN single crystals have a tetragonal structure, whereas polarized light microscopy and Raman scattering indicate a rhombohedral structure. Electron probe microanalysis shows the NBT single crystal is Na-deficient and slightly Bi-excess, while the NBT-KN single crystal is Na-deficient and slightly Bi-excess, slightly Nb-deficient and noticeably K-deficient. Temperature-controlled Raman scattering and measurement of the dielectric properties reveal that the characteristic phase transitions in NBT shift to lower temperatures on formation of a solid solution with KNbO3. The transitions indicated in the Raman scattering analysis can also be revealed by the impedance modeling parameters in terms of capacitance relaxations by diffusion mechanisms.