Mn-doped Na0.5K0.5NbO3 (NKN) crystals have been grown by self-flux method under several heat-treatment conditions. The cooling rate affected the quality of Mn-doped NKN crystals significantly. When the cooling rate was 0.5 oC/min at temperatures ranging from 1050 to 950 oC, the synthesized Mn-doped NKN crystal exhibited a single nucleation growth, compared with multinucleation growth when the cooling rate was 0.25 oC/min at temperatures ranging from 1050 to 950 oC. The frequency dependence on the ferroelectric P-E hysteresis loop of the Mn-doped NKN crystal was not observed at measurement frequency of 0.1 – 25 Hz. The annealed 0.5 mol% Mn-doped NKN crystal exhibited excellent P-E hysteresis loop with Pr of 45.0 μC/cm2 and Ec of 7.2 kV/cm.