An inherent conflict of (Bi0.5Na0.5)TiO3-based (BNT) lead-free piezoelectric ceramics is the optimizing piezoelectric response (d33) with deteriorating depolarization temperature (Td), which severely restricts the further achievements of BNT-based ceramics. A new strategy is proposed in this work to simultaneously realize high piezoelectric property (d33 = 140 pC/N) and thermal stability (Td = 232 °C) in BNT-based ceramics by integrating layered composite structure of 0.89(Bi0.5Na0.5)TiO3-0.11BaTiO3 with high Td and 0.87(Bi0.5Na0.5)TiO3-0.11BaTiO3-0.02(Sm0.5K0.5)TiO3 with large d33 (BNT1/BNT2) and thermal treatment processes. In the layered composite ceramics, the composition difference induces a built-in field (Eb) that promotes the diffusion of ferroelectric-relaxor (FE-RE) phase transition in the ceramics, delaying the Td to 185 °C. In addition, the thermal treatment processes facilitate both the Eb expansion, stabilize the d33 over a wide temperature range, as well as enlarge the grain size to elevate the d33 from 133 pC/N to 145 pC/N. Hence, the strategy we proposed is promising to offer a new paradigm for designing piezoelectric materials with high piezoelectric response over a wide temperature range.