Pentaerythritol bonded to cross-linked poly(vinylbenzyl chloride) beads (PE) provides a scaffold onto which ligands can be attached by reaction with reactive compounds such as phosphoryl halides. To broaden the applicability of PE for the preparation of ion-selective polymers, conditions are reported for the conversion of the hydroxyl group to the bromide, which acts as a better leaving group. The -CH2Br moiety thus provides a handle on which an array of ligands can be bound through nucleophilic substitution. In this first in a series of reports, immobilization of diethylamine onto the PE and the ion-binding affinities of the resulting polymer are described. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013