A branched polymer was prepared by grafting allyltrimethylammonium chloride onto polyvinyl alcohol (PVA) via free-radical polymerization. Afterwards, a series of hybrid membranes were prepared by sol-gel cross-linking between quaternary ammonium-PVA and tetraethoxysilane. The obtained membranes were characterized in terms of infrared spectroscopy, ion exchange capacity, water uptake, linear expansion ratio, and acid resistance. The thermal properties of the membranes were investigated as well. The diffusion dialysis performances of the membranes were tested by using a simulated feed solution containing HCl and FeCl 2 . The diffusion dialysis coefficients and the separation factors were much better than those of the commercial DF-120 membrane.