Thermal stabilizers are essential for polyvinyl chloride (PVC) processing. It is the emergence of thermal stabilizers that made PVC's applications migrate from laboratory to large‐scale industrial use. Herein we overview the development status of some traditional thermal stabilizers including lead salt, metal soaps, and organotin along with relatively newer thermal stabilizers such as organic thermal stabilizers and metal alkoxides. Taking into consideration the high market demand, opportunities for cost‐effective additives for thermal stabilizers are also briefly discussed. Finally, with the recent shift in focus on thermal stabilizer synthesis and their performance characterization but neglecting mechanical property testing and verification, we put forward application prospect of quantum chemical calculation for the development of PVC thermal stabilizers.