In pursuit for new reactive materials designed for synthesis of functional resins, the novel core-shell type polymeric supports with accessible chloromethyl groups were synthesized. The commercial Amberlite XAD-4 adsorbent was impregnated with different mixtures of vinylbenzylchloride and divinylbenzene, that were further polymerized in the structure of the polymer carrier. The syntheses have been evaluated by recording FT-IR spectra, capturing SEM micrographs as well as analyzing the sorption and desorption of nitrogen at 77 K. The amount of the introduced functionalities has been estimated by chlorine content determination. Based on the obtained results, the reactive chloromethyl groups were successfully introduced into XAD-4 structure. Captured SEM micrographs revealed that VBC/DVB copolymer has covered initial polymeric matrix of XAD-4 adsorbent. Based on the results we have determined conditions of the synthesis that allow us to receive that effect.