Single crystals of K 0.14 Na 0.86 NbO 3 (KNN) and Mn-substituted KNN (Mn-KNN, K 0.14 Na 0.86 Mn 0.005 Nb 0.995 O y ) were grown by a flux method, and the effects of Mn substitution on the leakage current, polarization and dielectric properties were investigated along [100] cubic . As-grown and annealed (850°C in air) crystals did not show an apparent polarization hysteresis loop due to its large leakage current density (³10 ¹3 A/cm 2 ). The annealing at 1100°C in air led to a marked decrease in leakage current density of the order of ³10 ¹6 A/cm 2 for KNN crystals. Mn-KNN crystals annealed at 1100°C in air exhibited a low leakage current density of ³10 ¹8 A/cm 2 . Electron spin resonance measurements and defect chemistry analysis show that the average valence increase of Mn by oxidation treatment (the annealing in air) absorbs electron hole, the carrier of the leakage current, which is suggested to be the origin of the low leakage current observed for Mn-KNN crystals.