Lead-free ceramics of Na0.5K0.5Nb1-xSbxO3 (NKNS) and Na0.5K0.5Nb1-xSbxO3 + 0.5 mol%MnO2 (NKNS + 0.5 mol%MnO2) (0 < x < 0.06) ceramics were prepared by a conventional solid-state hot pressing method. The ceramics possess a single-phase perovskite structure with orthorhombic symmetry. Microstructural examination revealed that Mn doping of NKNS leads to improvement of densification. The cubic-tetragonal and tetragonal-orthorhombic phase transitions of NKNS shifted to higher and lower temperature, respectively after introduction of Mn ion. Besides, ferroelectric and piezoelectric properties were improved. The results were discussed in term of difference in both ionic size and electronegativity of Nb5+ and Sb5+ and improvement of densification after Mn ion doping.