Sulfur, in general, exhibits excellent reactivity. Inverse vulcanization involves introducing monomers that can react with molten sulfur, drastically increasing the sulfur content compared to conventional vulcanization. This offers the advantage of developing materials with new properties not previously observed when various monomers are introduced. In this study, Diiodobenzene was chosen as a monomer, and through optimization of the polymerization reaction, it was confirmed that the sulfur content in the polysulfide-based network polymer can be controlled. This polysulfide material was found to possess exceptional elasticity, self-healing, and shape-memory capabilities that conventional materials lack. Particularly, its optical properties such as infrared transparency and photothermal effects make it suitable for future advanced applications such as 4D printing and shape morphing.