Novel magnetic chitosan/poly(vinyl alcohol) hydrogel beads (m-CS/PVA HBs) were prepared by an instantaneous gelation method and characterized by X-ray diffraction (XRD), vibrating sample magnetometry (VSM) and thermogravimetric analysis (TGA). Results of characterization indicated that m-CS/PVA HBs have been prepared successfully without damaging the crystal structure of Fe3O4 and their saturation magnetization were about 21.96 emu g(-1). The adsorption capacity of Congo Red on the m-CS/PVA HBs was 470.1 mg g(-1). The adsorption was well described by pseudo-second-order kinetics and Langmuir equation. Positive value of enthalpy change (Delta H degrees) (13.32 kJ mol(-1)) showed that the adsorption was endothermic and physical in nature. The values of Gibbs free energy change (Delta G degrees) were found to be -3.321 kJ mol(-1) at 298 K for m-CS/PVA HBs, indicating the spontaneity of Congo Red adsorption. Therefore, the m-CS/PVA HBs could be employed as a low-cost alternative to other adsorbents in the removal of dyes from aqueous solution. (C) 2011 Elsevier Ltd. All rights reserved.