Multilayer composite membranes with high removal capability for metal ion were prepared using electrostatic self-assembly (ESA) technique. Especially, self-assembled multilayer of chitosan microspheres and PAA were formed onto charged surface of polyacrylonitrile (PAN) membranes. It was confirmed that the alternate multilayer of chitosan and PAA were deposited on the base membrane surface. The formation of the ESA layer-bylayer of chitosan/PAA or chitosan microspheres/PAA onto the base membrane surface functionally equipped the membrane with removal capability for Cu2+. Especially, membranes with chitosan microspheres/PAA ESA layers on the surface showed relatively higher adsorption capability as compared with membranes with chitosan/PAA ESA layers. Besides, the influence of the pH of metal ion solution on the metal ion adsorption property of ESA modified membrane was investigated. It was proposed that the layer-by-layer self-assembled deposition of chitosan microspheres would be a new approach to functionalize membrane with high adsorption capability for metal ions.