Crystallization and morphology of polyethylene glycol with molecular weight M-n = 2000 (PEG2000) capped with cholesterol at one end (CS-PEG2000) and at both ends (CS-PEG2000-CS) were investigated. It is found that the bulky cholesteryl end group can retard crystallization rate and decrease crystallinity of PEG, especially for CS-PEG2000-CS. Isothermal crystallization kinetics shows that the Avrami exponent of CS-PEG2000 decreases as crystallization temperature (T-c). The Avrami exponent of CS-PEG2000-CS increases slightly with T-c, but it is lower than that of CS-PEG2000. Compared to the perfect spherulite morphology of PEG2000, CS-PEG2000 exhibits irregular and leaf-like spherulite morphology, while only needle-like crystals are observed in CS-PEG2000-CS. The linear growth rate of CS-PEG2000 shows a stronger dependence on T-c than PEG2000. The cholesterol end group alters not only the free energy of the folding surface, but also the temperature range of crystallization regime. The small angle X-ray scattering (SAXS) results show that lamellar structures are formed in all these three samples. By comparing the long periods obtained from SAXS with the theoretically calculated values, we find that the PEG chains are extended in PEG2000 and CS-PEG2000, but they are once-folded in CS-PEG2000-CS. (c) 2006 Wiley Periodicals, Inc.