AbstractThe hydroxylic end‐groups in the soluble fraction of poly(phenyl glycidyl ether) (PPGE) obtained with the aluminium isopropoxide (AIP)/ZnCl2 initiator system are studied using 19F NMR spectroscopy. Derivatization as trifluoroacetate esters affords poor structural information and handle difficulties. Hexafluoroacetone (HFA) hemiketalic adducts are much more easily prepared and offer more information, allowing not only to distinguish between primary and secondary alcohols but showing a clear sensitivity to the tacticity. This method is successful to calculate the percentage of hydroxylic end‐group in the polymer chain. In the case of an irregular PPGE sample, obtained with AIP alone as initiator, it is possible to identify three different hydroxylic end‐groups.