Interaction of beta-cyclodextrin (beta-CD) with alternating copolymers (pAdMA and pAdPhMA) of sodium maleate with adamantyl (Ad) and with adamantylphenyl (AdPh) vinyl ether has been investigated by several NMR techniques. Comparing the apparent association constants (K) for the polymers with the K for the model compounds, which are determined by the analysis of H-1 NMR and isothermal titration calorimetry data, respectively, the selectivities of beta-CD toward Ad and AdPh moieties are contrasting for the model and polymer systems. This phenomenon is described by circular dichroism and 2D NMR as follows; the most stable inclusion complex for the beta-CD/AdPh model system is extremely destabilized for the corresponding polymer system because of competition with hydrophobic interaction between neighboring AdPh moieties.