The structure and electrical properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 ceramic doped with 0.5 wt% of MnO were investigated in comparison with those of (Na0.5Bi0.5)0.94Ba0.06TiO3 ceramic. It was ascertained that the MnO addition did not cause remarkable change in crystal structure and microstructure. The MnO addition mainly displayed a hard effect on the electrical properties, an increase of coercive field (E) and mechanical quality factor (Qm) together with a decrease of dielectric constant (εr) and piezoelectric constant (d33). An enhancement of electromechanical coupling factor (kp) with the MnO addition was obtained too. An essential relation between the piezoelectric properties and ferroelectric nature of the ceramics was detected. It was found that the piezoelectric properties of the ceramics highly depended on the corporative contribution of remanent polarization (Pt) and coercive field.