A method is presented for preparing Merrifield-like resin beads starting from poly (vinyl chloride) (PVC) in spherical bead form. In this method, first, PVC is partially dehydrochlorinated in boiling methanolic KOH (20%) solution to create minute amounts of allylic carbon centers. Those centers trigger the un-zipping process and make further dehydrochlorination possible at relatively low temperatures (180-200 degrees C), while retaining the bead shapes. Acid catalyzed reaction of the dehydrochlorinated PVC particles with benzyl chloride at 180 degrees C yields crosslinked spherical bead polymers possessing chloromethyl benzene functions as high as 3.4 mmol g(-1). Experiments showed that, high yields of benzyl chloride insertions can be attained by using PVC samples with 40-50% of unsaturations. In the study transformation yields in each step were followed by conventional analytical methods and IR spectrometry. It was also demonstrated that modification of the chloromethyl groups either with KCN or sodium acetate proceeds with nearly quantitative yields, as in the case for chloromethylated styrene-divinyl benzene resins. (c) 2007 Elsevier Ltd. All rights reserved.