Lead-free ferroelectric single crystals of Na0.5Bi0.5TiO3 (NBT) and Mn-doped Na0.5Bi0.5TiO3 (Mn:NBT) have been grown by a top-seeded-solution growth method. The Mn concentration in the as-grown Mn:NBT crystal was determined to be 0.24 at.% by analytical analysis. X-ray diffraction studies revealed that both crystals had a phase transformational sequence of cubic (C)-> tetragonal (T)-> rhombohedral (R) on cooling, although the transition temperatures were decreased slightly by Mn doping. Polarized light microscopy images revealed that ferroelastic domains remained present below the T -> R phase boundary into the R phase field at room temperature for both NBT and Mn:NBT, although the ferroelastic domain size was decreased by a factor of similar to 2 x by Mn. We also found that the piezoelectric, ferroelectric and dielectric properties were enhanced in the R phase field by Mn.