Epichlorohydrin cross-linked chitosan microspheres (CS) and chitosan-heparin polyclectrolyte complex microspheres (CSH) were used in the adsorption of copper (II) ions in aqueous solution. The chitosan microspheres were prepared by the phase inversion method. The use of a cross-linking agent improNed the resistance to acidic medium. Polyelectrolyte complex microspheres were prepared by impregnating beparin in cross-linked chitosan microspheres. The microspheres were characterized by IR, TGA and DSC. A study on the effect of the pH on the adsorption of copper (11) ions showed that the optimum pH for both CS and CSH microspheres was 6.0. From a kinetic evaluation, it could be established that the adsorption equilibrium was achieved after 8 h for CS and 25 h for CSH microspheres. The adsorption isotherms were interpreted using Langmuir and Freundlich mathematical models. The results revealed that experimental data of CS was best adjusted by Langmuir model, with maximum capacity of surface saturation equal to 39.31 mg g(-1). On the other hand, Langmuir and Freundlich models provided a good fit for adsorption by CSH and the adsorption capacity was 81.04 mg g(-1). The interactions between copper (II) ions and both CS and CSH were confirmed by electron paramagnetic resonance spectroscopy, which revealed the formation of a square-planar complex with tetrahedral distortion on the surface of the adsorbents. (c) 2007 Elsevier Ltd. All rights reserved.