The 0.97(Na0.5K0.5)(Nb1−xSbx)O3‐0.03CaZrO3 ceramic with x = 0.09 exhibits a high d33 of 518 pC/N and a strain of 0.13% at 4.0 kV/mm owing to its orthorhombic‐pseudocubic polymorphic phase boundary (PPB) structure. However, these values decreased considerably above 90°C owing to its low Curie temperature (TC), indicating that its thermal stability is not sufficient for practical applications. Li2O was added to the specimen with x = 0.11 to improve its thermal stability of the strain and d33 by increasing the TC without degrading the actual d33 and strain values. The 0.97(Li0.04Na0.46K0.5)(Nb0.89Sb0.11)O3‐0.03CaZrO3 ceramic, having an orthorhombic‐tetragonal PPB structure, exhibits a d33 of 502 pC/N and a strain of 0.16%. This large strain was maintained up to 150°C and the d33 slightly decreased to 475 pC/N at 130°C. Therefore, this lead‐free ceramic displays excellent piezoelectric characteristics with improved thermal stability, indicating that it can be applied to piezoelectric actuators.