Lead-free piezoelectric ceramics (Bi0.94−x LaxNa0.94)0.5Ba0.06TiO3 have been fabricated by an ordinary sintering technique, and their piezoelectric and ferroelectric properties have been studied. The results of x-ray diffraction reveal that La3+ and Ba2+ diffuse into the Bi0.5Na0.5TiO3 lattices to form a new solid solution with a pure perovskite structure. After the partial substitution of La3+ for Bi3+ in the (Bi0.94−x Lax Na0.94)0.5Ba0.06TiO3 ceramics (x = 0–0.04), the ceramics exhibit a lower coercive field Ec and a larger remanent polarization Pr. Because of the large Pr and low Ec, the ceramics with x = 0.02–0.04 exhibit optimum piezoelectric properties: d33 = 181–196 pC N−1 and kP = 33.2–36.3%. The depolarization temperature Td decreases with increasing x (x = 0 − 0.04). At the high La3+ level (x = 0.06–0.12), the ceramics exhibit weak ferroelectricity and thus possess very poor piezoelectricity, and the low dielectric anomaly at Td disappears. In addition, the ceramics exhibit a relaxor characteristic, which probably results from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics with x = 0–0.04 may contain both polar and non-polar regions at temperatures above Td, while for the ceramics with x = 0.06–12, the polar and non-polar regions coexist at room temperature.