In this work, we mainly studied the effects of BiScO3 contents on the phase structure and electrical properties of lead-free (K,Na)NbO3-based ternary ceramics, and the material system of (0.97-x) K0.40N0.60NbO3-xBiScO(3)-0.03Bi(0.5)(Na0.6K0.3Li0.1)(0.5)HfO3 was prepared by the normal sintering method. The rhombohedral-tetragonal (R-T) phase boundary could be tuned in the ceramics by controlling BiScO3 contents. When the compositions approach the R-T phase boundary, the ceramics possess the enhancement of dielectric, ferroelectric and piezoelectric properties. The ceramics with x = 1.2% exhibited an excellent electrical behavior of d(33 )= 362 pC/N, k(p)similar to 0.42, P-r similar to 19.9 mu C/cm(2), epsilon(r)similar to 1671, and tan delta-0.02, which is assigned to the involvement of R-T phase boundary. Moreover, a high Curie temperature (T-C) of similar to 315 degrees C can be maintained even if the BiScO3 contents increase because of the addition of both BiScO3 and Li. As a result, the ceramics with x = 1.2% had both a large d(33) and a high T-C, showing that such a lead-free piezoelectric ternary system is suitable to the high-temperature applications. (C) 2018 Elsevier B.V. All rights reserved.