Polyene cyclization has emerged as a powerful tool for increasing molecular complexity. In recent years, gold-catalyzed polyene cyclization reactions have made significant progress, particularly in the total synthesis of complex polycyclic natural products with biological activity. Simultaneously constructing multiple stereogenic centers and core polycyclic ring structures, especially through the catalytic asymmetric reactions, greatly improves the efficiency of natural product synthesis. The alkynyl functional group can initiate polyene cyclization reactions, and the resulting vinyl moiety can facilitate subsequent functional group transformations, making it highly versatile. This review mainly summarizes the synthetic methodology of polyene cyclization reactions based on the underlying mechanisms and their applications in the total synthesis of polycyclic natural products.