Six arm poly(ethylene oxide) (PEO) stars carrying either 6 pyridyl or 12 hydroxyl groups at their periphery were synthesized using an arm-first approach. To this end, two novel alpha,omega-heterodifunctional PEO's, namely alpha-ketal,omega-hydroxy and alpha-pyridyl,omega-hydroxy PEO's were synthesized and, after the deprotonation of their hydroxyls, deactivated onto hexachlorocyclophosphazene which served to build the core. Quaternization of the stars containing six outer pyridyl groups created positive charges at their periphery while the acidic treatment of stars carrying terminal ketal rings afforded six arm PEO stars with 12 peripheral hydroxyls. The latter compound was subsequently deprotonated and used to polymerize ethylene oxide by a classical core-first approach. This resulted in the formation of highly branched PEO's also referred to as dendrimer-like PEO stars which consisted of a first generation of six PEO arms and a second generation of 12 hydroxy-ended PEO branches. (C) 2003 Elsevier Ltd. All rights reserved.