New lead-free ceramics (Bi0.92Na0.92-xLix)(0.5)Ba0.06Sr0.02TiO3 have been fabricated by a conventional ceramic technique and their electrical properties have been studied. X-ray diffraction studies reveal that Li+, Ba2+ and Sr2+ diffuse into the Bi0.5Na0.5TiO3 lattices to form a new solid solution with a pure perovskite structure. The partial substitution of Li+ for Na+ increases the remanent polarization P-r of the ceramics. Because of the large P-r and low coercive field E-c, the ceramics with x = 0.075-0.125 exhibit excellent piezoelectric properties: d(33) = 189-235 pC/N, k(p) = 33.6-36.3% and k(t) = 51.6-54.3%. The ceramics exhibit relaxor behaviors after the substitution of Li+ for Na+. Our results also suggest that polar and non-polar phases may coexist in the ceramics at temperatures above the depolarization temperature T-d. (C) 2010 Elsevier B.V. All rights reserved.