Two-dimensional layered structural materials exhibit a wide range of properties due to their ultrahigh specific surface area. However, achieving ordered exfoliation to obtain uniform two-dimensional structures remains challenging. In this study, we developed a supramolecular system by covalently bonding hexathiobenzene (HB) into β-cyclodextrin to create a light-responsive moiety, followed by coassembly with bipyridine and nickel ions to form a polypseudorotaxane (PR) system, which enables an in situ light-induced exfoliation strategy for two-dimensional materials. By further introducing an appropriate ratio of ethanol and applying in situ light irradiation, the gradual evaporation of the solvent ultimately led to the uniform formation of bilayer PR two-dimensional materials. This strategy provides a novel and effective approach for the preparation of two-dimensional layered structural materials from the light perspective.