A series of polypseudorotaxanes were synthesized from alpha-cyclodextrins (alpha-CDs) threaded onto photopolymerizable CL-PEG-CL oligomers bearing acrylate terminals. The corresponding supramolecular structured hydrogels were prepared from these polypseudorotaxanes in a mixed solvent of H2O and DMSO via in situ photopolymerization under UV irradiation. The structure and properties of the gels were characterized by FTIR, TGA-DTG and WAXD. The results show that alpha-CDs are threaded and immobilized onto the network chains of the hydrogel with crosslinking junctions as stoppers topologically, and the feed molar ratio of alpha-CDs to the macromers affects the hydrogel structure and the water distribution in the hydrogel. These supramolecular structured hydrogels may be good candidates for biomaterial applications. (C) 2003 Elsevier Ltd. All rights reserved.