Glutaraldehyde cross-linked Poly (vinyl alcohol)/Polyvinylamine (PVA/PVAm) membranes for removal of metal ions from aqueous solution were prepared by solution casting and solvent evaporation techniques. The membranes were characterized using XRD, Swelling studies and metal ions adsorption experiments. The results show that PVA/PVAm membranes exhibit semi-crystalline natures as PVA macromolecular, however, the degree of crystallinity of membranes decrease as PVAm increased. The membranes were pH-sensitive and the swelling ability of membranes was significantly enhanced. It was found that the change of swelling behavior versus pH was consistent with the change of degree of ionization versus pH. The amount of Cu2+ ions adsorbed increased as PVAm increased as well as increasing pH of solution in the range of 2.5~6.0.