The construction procedure and structure of Ni2+ macromolecular complexes with series of poly styrene and maleic anhydride (PSt/MA) were studied. Both the copolymers and the complexes (Ni-PSt/MA) were characterized by means of FTIR, elemental analysis, gel permeation chromatography (GPC) and atomic adsorption spectrometer (AAS). A further study using PSt/MA as chelating resin to recover Ni2+ was performed. The adsorption behavior for Ni2+ and various relating parameters of PSt/MA in the separation process were determined. The results indicate that the adsorption capability varies with pH values and the PSt/MA can recover Ni2+ in higher adsorption rate and higher selective coefficient from a mixed solution containing light metals such as Ca2+ and Mg2+ impurities.