In the anionic polymerization of phenyl glycidyl ether (PGE) initiated by sodium caprolactam (NaCL) or sodium caprolactam/N-acetyl caprolactam (NaCL/AcCL), oligo(hydroxy ethers) with different structures and distributions are formed depending on the temperature and concentration of the initiating system. The progress of the reaction was followed by using epoxide titration and high-performance liquid chromatography. The properties of the reaction products were determined by means of vapour-phase osmometry. The melting ranges of the isolated products were found to be from 72 to 120 degrees C and molar masses from 340 to 4000 g mol(-1).