Abstract: Silicone rubber foam materials exhibit promising application prospects in electronics, construction, automotive, aerospace, new energy, medical, and packaging fields. The cellular structure and formation of cross-linked networks play a critical role in determining their performance. This paper reviews recent advancements in regulating the cellular structure of silicone rubber foam through vulcanization systems and its subsequent impact on mechanical properties. From the perspective of vulcanizing agents, the applications of peroxides, sulfur, and hydrogen-containing silicone oils in vulcanized silicone rubber are discussed. Furthermore, the effects of single and compounded vulcanization systems on cellular structure and mechanical performance during foam preparation are analyzed. Finally, future directions for optimizing cellular structure regulation via vulcanization systems are proposed, emphasizing trends such as green chemistry, high-performance formulations, and intelligent manufacturing.