As a candidate for lead-free piezoelectric materials, Li2O excess 0.95(Na0.5K0.5)NbO3–0.05LiTaO3 (NKN-5LT) ceramics were developed by conventional sintering process. Sintering temperature was lowered by adding Li2O as a sintering aid. Abnormal grain growth in NKN-5LT ceramics was observed with varying Li2O content. In the 1 mol% Li2O excess NKN-5LT samples sintered at 1000°C for 4 h in air, electromechanical coupling factor and piezoelectric constant of NKN-5LT ceramics were found to reach the highest values of 0.37 and 250 pC/N, respectively. Lead-free piezoelectric ceramic, Li2O excess NKN-5LT, multilayer ceramic actuators (MLCA) were fabricated. 10 × 10 × 1 mm3 size MLCAs were fabricated by conventional tape casting method. The displacement of Li2O excess NKN-5LT MLCA with 3 mm thickness was ~1 μm at 150 V.