For potassium-sodium niobate, the piezoelectric constant (d33) was usually improved by sacrificing the Curie temperature (TC). In this work, a material system of 0.992(K0.46Na0.54)0.965Li0.035Nb(1-x)Sb(x)O3-0.008BiScO3 has been designed and prepared with the aim of achieving both a large d33 and a high TC at the same time. The chemical compositions are found to be homogeneously distributed in the ceramics. The introduction of Sc is found to be responsible for different grain sizes. The rhombohedral-tetragonal phase coexistence zone lies in the composition range of 0.02<x ≤ 0.06. The ceramic is thermally stable in terms of ferroelectric properties. The change in the domain-wall activities induced by the configuration variation of defect dipoles upon annealing is believed to be responsible for the variation in the d33 at different temperatures. The ceramic with x = 0.025 shows a good comprehensive performance of d33 ≈ 325 pC/N and k(p) ≈ 48%, together with a high T(C) of ~358 °C, demonstrating that this material system is a promising candidate for high-temperature piezoelectric applications.