Amphiphilic hemi-telechelic and telechelic poly(ethylene oxide) (PEO) hybrids based on polyhedral oligmeric silsesquioxane (PUSS) were prepared via the copper-catalyzed azide-alkyne "click" reaction. Thermal properties of POSS-PEO were characterized using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The result shows that the thermal properties of telechelic POSS-PEO are effectively enhanced by POSS. The morphology of the PUSS-containing PEO hybrid crystals was investigated using polarized optical microscopy (POM), and the results indicate that it is much easier for the PUSS in the telechelic POSS-PEO hybrids (T-POSS-PEO) to form quite large aggregates, which act as nucleating agents during the crystallization of the PEO chains. The self-assembly behavior of POSS-PEO in water was also studied using transmission electron microscopy (TEM). The results reveal that hemi-telechelic POSS-PEO hybrids (HT-POSS-PEO) can self-assemble into spherical aggregates, whereas the T-POSS-PEO hybrids self-assemble into ellipsoidal aggregates. (c) 2012 Elsevier Ltd. All rights reserved.