A new group of ABO3-type lead-free piezoelectric ceramics, [Bi0.5(Na1-xAgx)0.5]1-yBayTiO3, was developed, and the corresponding invention patent was submitted. The ceramics were synthesized by the conventional ceramic sintering technique using electronic grade raw materials, and the preparation techniques are very stable and convenient. The crystalline phase, microstructure and electric properties of the ceramics were also investigated. All the ceramics have high densities of about 5.70–5.84 g/cm3, which are more than 95% of the theoretical values. This system provides high piezoelectric performances: d33=168 pC/N, kp=0.31 when x=0.06, y=0.06. Moreover, the samples doped with a moderate amount of Mn could increase the mechanical quality factor Qm and reduce the dielectric loss tgδ simultaneously. The temperature dependence of piezoelectric properties measured show that at up to 180°C, d33 can still remain 126 pC/N for [Bi0.5(Na0.96Ag0.04)0.5]0.90Ba0.10TiO3 ceramics, which has a d33 of 137 pC/N at room temperature.