Bi2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 (BNBT6) lead-free piezoelectric ceramics were fabricated by a conventional sintering technique. The effects of Bi2O3 on the piezoelectric properties and microstructures of the doped BNBT6 were investigated. X-ray diffraction analysis showed that a solid solution was formed when Bi2O3 diffused into BNBT6 lattice and the crystal structure of the sintered hybrid changed from rhombohedral to tetragonal symmetry with increasing Bi2O3 amount. Piezoelectric and dielectric properties measurements revealed that doping Bi2O3 within a certain range enhanced the piezoelectric coefficient (d33), electromechanical coupling factor (kp), relative dielectric constant (ε33 T/ε0), and dielectric loss (tanδ). When 3mol% Bi2O3 was doped, both d33 and kp of the ceramics reached their maxima, 165pC/N and 24%, respectively.