The introduction of methacrylic, carboxylic and phosphate functional groups on the core and at the end of the poly(ethylene oxide) (PEO) arms in the PEO star-shaped polymers is described. In the polyglycidol (PGL) star-shaped polymers phosphate groups were attached to the PGL arms as side groups. Polymers were characterized by NMR and SEC analysis with triple detection. The conversion of the unsubstituted star-shaped polymers into functionalized has been confirmed by H-1 and C-13 NMR spectra. The influence of the length of arms, their structure and the presence of functional groups on melting (T-m) and crystallization (T-c) temperatures and the degree of crystallinity (X-c) by differential scanning calorimetry (DSC) has been studied. (C) 2008 Elsevier Ltd. All rights reserved.