The structure, dielectric and piezoelectric properties of 0.96(Bi 0.5 Na 0.5 )TiO 3 -(0.04-x)BaTiO 3 -xLiNbO 3 (x ¼ 0, 0.01, 0.02, 0.03, 0.04) ceramics were investigated by a conventional solid-state reaction method. All compositions show a single perovskite structure without any second phases. It was ascertained that the morphotropic phase boundary (MPB) of ferroelectric rhombohedral and relaxor tetragonal lies in the range of 0.02 x 0.04 at room temperature. As a result, the MPB compositions show improved properties; the saturated polarization, remnant polarization and coercive field are 43.7 μC/cm 2 , 38.7 μC/cm 2 and 48.7 kV/cm for x ¼ 0.02 and 43 μC/cm 2 , 37.9 μC/cm 2 and 47 kV/cm for x ¼ 0.03, respectively. The maximum of piezoelectric constant d 33 (124pC/N) was obtained for the ceramic with x ¼ 0.03, which was located at the MPB region. Our results do not only supplement for BNT-based lead-free piezoelectric ceramics but also provide a way to develop new high-performance Pb-free piezoceramics.