Novel supramolecular polymers have been prepared from a beta-cyclodextrin dimer and a ditopic guest dimer having adamantyl groups. beta-Cyclodextrins were bound to poly(ethylene glycol) (PEG, M-n 600). Adamantyl groups were also bound to PEG (Mn 600). The ROESY NMR spectrum of a 1:1 mixture of the beta-cyclodextrin dimer and the ditopic adamantane guest dimer showed ROE correlations between the protons of adamantyl substituents and the inner protons of beta-cyclodextrin. Molecular weights and molecular sizes of the supramolecular polymer constructed by the mixture of the beta-cyclodextrin dimer and the ditopic adamantane guest dimer were investigated by the pulse field gradient spin echo (PFGSE) NMR and by vapor pressure osmometry (VPO). The results have shown that the mixture of the beta-cyclodextrin host dimer and the adamantane guest dimer gave linear supramolecular polymers with high molecular weight (M-n = 100 000).