Na-23 NMR spectroscopy was used to study complexation of sodium cations (NaClO4) with a few of star-shaped polyethers. The bonding of sodium ions by these polymers having PEO arms and with model compounds has been studied in anhydrous methanol solutions. In this paper the preliminary studies are presented, indicating that star polymers built from PEO arms and core formed from diepoxides, containing cyclic structures, are good polydentate complexing agents of sodium cations. Core cyclic structures hinder exchange of the complexed sodium cation with free cations. (C) 2016 Elsevier Ltd. All rights reserved.