Poly(neopentyl glycol sebacate) (PNGS) is able to form inclusion complexes with three cyclodextrins (alpha -CD, beta -CD, and gamma -CD). The complexes are characterized by XRD, C-13 CP/MAS NMR, FTIR, H-1 NMR, and TGA. The complexes possess a column structure wherein some structural change occurs when the "raw" gamma -CD/PNGS complex is washed and dried. It is suggested that alpha -CD can "squeeze" over the bulky dimethyl groups and settle on and complex the thinner part of the polymer chain.