La2O3-doped lead-free 0.82Bi0.5Na0.5TiO3-0.18Bi0.5K0.5TiO3 (abbreviated to 0.82BNT-0.18BKT) piezoelectric ceramics were synthesized by the conventional mixed-oxide method, and the effect of La2O3 addition on the dielectric and piezoelectric properties was investigated. X-ray diffraction (XRD) patterns show that La2O3 diffuses into the lattice of the 0.82BNT-0.18BKT ceramics to form a solid solution with a pure perovskite structure. SEM images indicate that the grain size of the 0.82BNT-0.18BKT ceramics increased with the addition of La2O3 doping. The electrical properties of 0.82BNT-0.18BKT ceramics have been greatly improved by certain amount of La2O3 substitutions. At room temperature, the 0.82BNT-0.18BKT ceramics doped with 0.25 wt. % La2O3 exhibited the optimum properties with high piezoelectric constant (d33 = 142 pC/N) and high planar coupling factor (kp = 0.23).