One of the (Bi1/2Na1/2)TiO3 (BNT)-based solid solutions, Ba-modified bismuth sodium titanate, (Bi1/2Na1/2)1-x Ba x TiO3 (BNBT), is studied for its dielectric and piezoelectric properties as a new group of lead-free piezoelectric ceramics. A rhombohedral (Fα)-tetragonal (Fβ) morphotropic phase boundary (MPB) is shown to exist at x=0.06∼0.07 by X-ray data, and dielectric and piezoelectric properties. BNBT ceramics with the MPB composition are superior as piezoelectric ceramics in high-frequency ultrasonic applications or as piezoelectric actuator materials because of a lower free permittivity, ε33 T/ε0, and a high electromechanical coupling factor, k t or k 33, along with high mechanical strength.