α-CYCLODEXTRIN (α-CD, cyclohexaamylose) is a cyclic molecule consisting of six α(1→4) linked glucose residues. Because of its annular structure it can form inclusion complexes with a wide variety of guest molecules even in aqueous solution and has been studied as an enzyme model1. The structure of the ‘empty’ water adduct suggests a release of conformational and intramolecular hydrogen bonding energy of the α-CD molecule when complex formation occurs2,3. To study this process in more detail, we have investigated the adduct with methanol.