Environmentally friendly lead-free piezoelectric materials have been attracting significant attention in recent years. Na1/2Bi1/2TiO3-based relaxor ferroelectrics have found acceptance for application in promising lead-free transducers in high-power ultrasonic devices. However, their low thermal stability, i.e., their relatively low ferroelectric-relaxor transition temperature (TF-R), hinders their practical application. Herein, a thermal-quenching approach is applied on a Na1/2Bi1/2TiO3 (NBT)-based single crystal, which yields a large increase in TF-R and dramatic enhancement of its ferroelectric ordering, leading to excellent thermal stability of its dielectric, ferroelectric, and piezoelectric properties. This behavior is mainly attributed to quenching-induced domain evolution as well as its octahedral tilt, which is linked to the increased oxygen vacancies. The substitution of long-range ordered ferroelectric domains for short-range polar nanodomains contributes to its increased coherence length and, consequently, enhancement of TF-R. This work provides an approach to the optimization of the ferroelectric ordering and thermal stability of NBT as well as an in-depth understanding of the quenching effect on the local structure, which could be applied to other relaxor-based ferroelectrics for optimization of their macroscopic properties.