Macroporous chitosan/poly(vinyl alcohol) membrane adsorbents were synthesized by solvent evaporation in the presence of poly(ethylene glycol) which was utilized as porogen. The membranes were applied for Cu(II) ion adsorption from water. SEM, AFM and wettability analyses were performed for membrane characterization. Insertion of poly(ethylene glycol) generated macrovoids in the dense structure of CS/PVA membranes through particulate leaching out mechanism. According to the static adsorption tests, the uptake capacity of the porous membranes is elevated (similar to 26 mg/g) compared to that of the dense membranes (similar to 10 mg/g). This phenomenon is attributed to the increase in the density of active sites, water affinity and surface roughness as a result of the porogen effects. The approachability of the ions to the active sites was also affected by these important parameters. Both size and density of the macrovoids increased with increasing PEG content from nil to 5 wt%. Fragility of the resultant porous structures prohibited synthesizing CS/PVA membranes with higher porogen contents. Desorption tests showed that the porous membranes were better regenerated in comparison to the dense membranes using Na(2)EDTA as eluant. Generally, the results suggested that the CS/PVA membranes, comprising PEG as pore-generator agent, are potential candidates for adsorption and elimination of Cu(II) ions from water. (C) 2013 Elsevier B.V. All rights reserved.