High-performance lead-free piezoelectrics (d33 > 400 pC/N) based on 0.96(K0.5Na0.5)0.95Li0.05Nb1-xSbxO3-0.04BaZrO3 with the rhombohedral-tetragonal (R-T) phase boundary have been designed and prepared. The R-T phase boundary lies the composition range of 0.04 ≤ x ≤ 0.07, and the dielectric and piezoelectric properties of the ceramics with the compositions near the phase boundary are significantly enhanced. In addition, the ceramic with x = 0.07 has a giant d33 of ~425 pC/N, which is comparable to that (~416 pC/N) of textured KNN-based ceramics (Saito, Y.; Takao, H.; Tani, T.; Nonoyama, T.; Takatori, K.; Homma, T.; Nagaya, T.; Nakamura, M. Nature 2004, 432, 84). The underlying physical mechanisms for enhanced piezoelectric properties are addressed. We believe that the material system is the most promising lead-free piezoelectric candidates for the practical applications.