Microstructural details of poly(phenyl glycidyl ether) (PPGE) and its optically active form obtained by the aluminium isopropoxide (AIP)/ZnCl2 ionic-coordinative initiator were analysed by nuclear magnetic resonance techniques. In order to assign the soluble fraction signals unmistakably, PPGE samples had to be synthesized using various cationic initiator systems. Several modifications were studied in the AIP/ZnCl2 initiator system (such as the use of various zinc salts and the addition of water) and the tacticity and irregularity contents of the polymers were determined.