Ternary multisilicon copolymers are prepared from copolymerization of acrylic acid, sodium styrene sulfonate and gamma-methacryloxypropyl trimethoxy silane, from which functional groups of -Si(OCH3)(3), -COOH and -SO3Na are obtained respectively. The acidic -COOH groups may induce gel during copolymerization, and thus sufficient solvent needs to be used. The -Si(OCH3)(3) groups can crosslink with polyvinyl alcohol (PVA) to yield cation exchange hybrid membranes. The membranes have the ion exchange capacity of 1.01-2.26 mmol/g, water uptake of 39.1-59.7%, swelling degrees of 108-339% in 65 degrees C water after 192 h, and swelling degrees of 254-344% in 65 degrees C alkaline solution after 60 h. Membrane with proper ratios of multi-functional groups can sorb 1.4 mol/L NaOH in 1.0 mol/L NaOH solution. The membranes are used in diffusion dialysis (DD) process for alkali recovery from NaOH/Na2WO4 solution. The dialysis coefficients of NaOH (U-OH) are in the range of 0.013-0.021 m/h at room temperature, with the separation factors of 15-23. The high U-OH values indicate the superiority of multi-functional groups. The -OH, -COOH and -SO3Na groups from PVA and multisilicon copolymer chains may have coupling effects on the transport of both Na+ and OH- ions. (C) 2014 Elsevier B.V. All rights reserved.