A series of supramolecular inclusion complex (IC) films were formed by threading a-cyclodextrin (a-CD) molecules over poly(ethylene glycol) (PEG), according to the designed ratio of a-CD/PEG. Because of containing a-CD-PEG inclusion crystallites as physical crosslinks and uncovered PEG crystallites as ‘‘switch phase’’, the resulting supramolecular a-CD-PEG partial ICs displayed a shape memory effect. The properties of the materials were investigated by 1H-NMR, X-ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and swelling measurement. It was found that the casting temperature, solvent, and the ratio of a-CD-PEG inclusion/PEG had great influence on the formation and properties of a-CD-PEG partial ICs. The modes of complexes on different conditions were proposed.