Lead-free (1−x−y)Bi 0.5 Na 0.5 TiO 3 –xBaTiO 3 –yBi 0.5 Ag 0.5 TiO 3 (BNT–BT–BAT-x/y, x=0–0.10, y=0–0.075) piezoelectric ceramics were synthesized by conventional oxide-mixed method. The microstructure, ferroelectric, and piezoelectric properties of the ceramics were investigated. Results show that a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases of BNT–BT–BAT-x/0.04 ceramics is formed at x=0.06–0.08. The addition of BAT has no obvious change on the crystal structure of BNT–BT ceramics while it causes the grain size of the ceramics to become more homogenous. Near the MPB, the ceramics with x=0.06 and y=0.05–0.06 possess optimum electrical properties: P r ∼42.5μC/cm 2 , E c ∼32.0kV/cm, d 33 ∼172pC/N, k p ∼32.6%, and k t ∼52.6%. The temperature dependences of k p and polarization versus electric hysteresis loops reveal that the depolarization temperature (T d ) of BNT–BT–BAT-0.06/y ceramics decreases with increasing y. In addition, the polar and non-polar phases may coexist in the BNT–BT–BAT-x/y ceramics above T d .