Li+ and Ta5+ modified lead-free piezoelectric ceramics [(K0.5Na0.5)1-xLix](Nb1-yTay)O3 have been prepared by an ordinary sintering technique. Effect of Li+ and Ta5+ on microstructure and piezoelectric properties of the ceramics was systematically studied. A morphotropic phase boundary between orthorhombic and tetragonal phases is identified in the composition range of (0.02≤x≤0.04, 0.15≤y≤0.25), which can enhance electrical properties of [(K0.5Na0.5)1-xLix](Nb1-yTay)O3 ceramics. The Curie temperature TC of these ceramics is lower than that of pure (K0.5Na0.5)NbO3 ceramics, but the temperature of orthorhombic to tetragonal phase transition TO-T of the former is higher than that of the latter. TC and TO-T both decrease as the content of Ta5+ increases. With the addition of Li+ increasing, TC increases. The optimal piezoelectric properties are obtained at (x, y)=(0.03, 0.20): piezoelectric constant d33 is 192pC/N; the electromechanical coefficient of the planar mode kp is 44%; room temperature dielectric constant εr is 1049, and the corresponding mechanical quality factor Qm is 49.