The EPR spectra of composite dextran and carboxymethyldextran gels were studied in order to identify the functional groups involved in copper(II) complexation depending on pH. The porous structure resulting from crosslinking of polymer chains of dextran, via epichlorohydrin, forces the immobilization of Cu2+ ions surrounded by different oxygen groups of the polymer gel matrix. The different polynuclear structures are postulated to be formed depending on the type of polysaccharide derivatives. The results indicate that carboxyl and deprotonated hydroxyl groups participate in the complex formation.