The influence of poling temperature (Tp) on d33 and of (Na0.52K0.4425Li0.0375)(Nb0.86Ta0.06Sb0.08)O3 ceramics is investigated. No notable stress is induced as there is not apparent phase transition on cooling when the ceramics are poled below orthorhombic-tetragonal phase transition temperature (To–t). However, stress emerges by phase transition when poled above To–t leading to degrade d33. Consequently, the ceramics poled near To–t exhibit the best d33 of 350 pC N−1. In addition, , derived from intrinsic and extrinsic contributions, remains about the same with Tp because the ultrafine, lamellar domains could easily respond to an external electric field.