(Na0.5Bi0.5)0.94Ba0.06TiO3 (NBBT) ceramics doped with 0.1∼2.0 mol.% Ba (Zr0.05Ti0.95)O3 were investigated in terms of the sintering, microstructure, phase transition, and piezoelectric properties. BZT doping has no remarkable effect on the microstructure and densification within the studied doping content. Up to 2 mol.% BZT can dissolve into the lattice of NBBT ceramics, and the structure symmetry is not changed. However, a significant change in the piezoelectric properties took place. The piezoelectric coefficient d33 for the 0.1 wt.% BZT-doped NBBT ceramics sintered at 1150 °C was found to be 120 pC/N and the electromechanical coupling factor kp = 0.24.