(Na1-xBax)(Nb1-xTix)O3 (NNBTx; x=0.0-0.21) solid-solution ceramics were synthesized and their crystal structure, dielectric properties and piezoelectric properties were investigated. The crystal structure at room temperature of NNBTx varied from orthorhombic to tetragonal with increasing BaTiO3 content x. The phase boundary between orthorhombic and tetragonal at room temperature was confirmed BT content between x=0.08 and 0.09. For x>0.05, it was found that the Curie temperature was decreased with increasing x. The highest electromechanical coupling factor, kp, and the largest piezoelectric constant, d33, were obtained at x=0.09-0.10.