Lead-free (K0.5Na0.5)NbO3-LiNbO3 (KNN-LN) and (K0.5Na0.5)NbO3-LiTaO3 (KNN-LT) ferroelectric single crystals, with the dimensions of 11 ´ 11 ´ 5 mm3 and 5 ´ 5 ´ 3 mm3, were grown successfully using the top-seeded solution growth (TSSG) method, respectively. The crystal structures were analyzed by means of X-ray diffraction, showing orthorhombic symmetry for KNN-LN single crystals and coexistence of orthorhombic and tetragonal symmetry for KNN-LT single crystals at room temperature. The orthorhombic-tetragonal (TO-T) and tetragonal-cubic (TC) phase transition temperatures are 195 °C and 420 °C for the KNN-LN single crystals, and 130 °C and 280 °C for KNN-LT single crystals, respectively. The remnant polarization (Pr) is 27.8 μC/cm2 with a coercive field (Ec) of 17 kV/cm for KNN-LT single crystals. The two single crystals showed 90° domains with layers in (parallel) straight lines, while KNN-LT single crystals have a larger domain region. The actual stoichiometry deviates easily from the original composition in the process of crystal growth, thus, an appropriate nominal composition and optimized crystal growth method is desired to get high-quality crystals in the future.