In this paper, we demonstrate the first hybrid suprastructure of pseudopolyrotaxanes (PPRs) on clay nanoplatelets. Simple end-modification of poly(ethylene glycol) with pyridinium (PEG-N(+)) enabled the chains to form brushlike conformation on clay surfaces. Thus, the PEG chains were able to thread into the cavities of alpha-cyclodextrins (alpha-CDs), leading to hybrid PPR hydrogels. This was very different from the unmodified PEG chains, which were absorbed onto the clay surface and thus made the PPR formation impossible. The hydrogels made of this PPR-on-clay structure displayed a dynamic modulus 1 order of magnitude higher than those of the native PPR hydrogels. Furthermore, based on the competitive host-guest interactions, such hybrid hydrogels showed fully photoreversible sol-gel transition after a competitive guest containing azobenzene moiety was introduced.