An amino derivative of beta-cyclodextrin [6-(6-aminehexanamide)-6-deoxy-beta-cyclodextrin (6-beta CD)] was synthesized, and the formation of an intramolecular inclusion complex was studied by NMR techniques. The deprotonation/protonation of the amino group stimulates an in/out movement of the pendant group toward/from the cyclodextrin cavity, the protonated species lying outside the hydrophobic cyclodextrin cavity but the unprotonated one residing inside and outside the cavity. The protonation of the amino group is a fast exchange rate NMR time-scale process, but the chain movement is a slow one. The equilibrium constants of both processes were determined from H-1 NMR experiments and the kinetic constants for the slow process were determined from exchange spectroscopy (EXSY) experiments.