A new silica gel compound modified 4,4′-oxy-bis(chlorophenylglyoxime) (CPGO) was synthesized and characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. The sorption capacity of such a matrix towards Co(II), Ni(II) and Cu(II) from aqueous solutions was studied. The optimum pH values for the separation of these divalent cations on the sorbent were 5.0, 6.0 and 6.0 for Cu, Co and Ni, respectively. The process of metal separation was followed by batch method, and fitted to a Langmuir and Freundlich sorption isotherms. The maximum sorption capacities (0.055, 0.042, and 0.034 mmol g-1) were found from the Langmuir equation and the enthalpies of binding were 44.96, 71.63, and 68.14 kJ mol-1 for Cu, Co and Ni, respectively. The other thermodynamic parameters calculated from the adsorption results were used to explain the mechanism of the adsorption. For example, the Gibbs free energies of binding agree with the spontaneity of the proposed reaction between cations and basic centers. © 2009 Elsevier B.V. All rights reserved.