The slightly water-soluble β-CD and its crystalline inclusion complexes with different molecular weights of poly( ethylene glycol), abbreviated as PEG, were prepared and characterized. The results show that the β -CD forms a crystalline inclusion complex with PEG (MW 600) and PEG (MW 1500) in the solid state. In the solution state, 2D NMR spectroscopy, shows that the PEG is present in the cavity of the P-CD. Coherent cross peaks were observed in both 2D NMR NOESY and ROESY showing correlation between the inner and outer protons of β -CD with the repeating unit of PEG. Scanning electron microscopy (SEM) shows the formation water soluble crystalline complexes between the β -CD with the amorphous PEG (MW 600) and PEG (MW 1500). Crystal formation was supported by wide angle X-Ray studies, W AXD. W AXD patterns for the β-CD/PEG crystalline complexes show new peaks indicative of formation of structures different from the crystalline β-CD.