Host-guest complexes of alpha-cyclodextrin (alpha-CD) and methylated beta-cyclodextrin (Me-beta-CD) with diacrylates and dimethacrylates of butan-1,4-diol and hexan-1,6-diol at varying stoichiometries were studied. The complexes were analyzed by means of H-1 NMR, two-dimensional ROESY spectroscopy and Job's curves, which clearly revealed the discriminating influence of the two hosts towards complex formation. The corresponding polymers were obtained using a redox initiator system in water. Thermal analysis and IR measurements of the polymers provided evidence for the existence of a polyrotaxane architecture.