We report the first preparation of a supramolecular polysulfide polymer, which is a polyrotaxane containing sulfur-styrene copolymer and methylated α-cyclodextrins (TMαCDs) as linear and cyclic molecules, respectively (SPRx). Compared to the sulfur-styrene copolymer prepared by a copolymerization method typically used to synthesize polysulfide polymers, the environmental and thermal stabilities of SPRx are significantly improved because the polysulfide polymer is covered with TMαCD.