Novel high molecular weight copolymers of ethylene oxide (EO) and glycidol or ethoxy ethyl glycidyl ether (EEGE) were obtained via suspension anionic coordination polymerization using calcium amide-alkoxide initiating system. H-1 and C-13 NMR spectroscopy were used for the structural characterization of the copolymers as well as for the determination of the molar content (up to 2 mot%) of the functional monomers incorporated into the PEO backbone. SEC measurements of the copolymers determined (M) over bar (n). in the range of (2-11) x 10(5) g/mol. Surprisingly low polydispersity values of average (M) over bar (w)/(M) over bar (n) = 1.5 were obtained for the EO/EEGE copolymers. The calcium amide-alkoxide initiated polymerization of EEGE resulted in high molecular weight polymers with relatively broad polydispersity values ((M) over bar (n) = (0.8-1.5) x 10(5) g/mol, (M) over bar (w)/(M) over bar (n) less than or equal to 4.2). EO/glycidol copolymers and polyglycidol were obtained after cleavage of the acetal protecting group of the EEGE units. Polymers with hydrophilic backbone bearing hydrophobic stearyl moieties were obtained after modification of EO/glycidol copolymers with stearic acid. Their associating properties in aqueous solution were studied. Increasing either temperature or polymer concentration induces aggregate formation.