This paper describes the preparation of the metallic affinity column by atom transfer radical polymerization of glycidyl methacrylate (GMA) on Wang resin surface. The metallic ions (Zr4+, Fe3+, and Pd2+) were introduced after phosphonation of the epoxy group of the grafted poly(GMA) on Wang resin surface. The successful results on metallic ion-immobilized polymeric microsphere stationary phase were confirmed via Fourier transform infrared, scanning electron microscopy, X-ray photoelectron spectra (XPS), and inductively coupled plasma-atomic emission spectrometer. The resolution degree of the phos phonated casein and dephosphonated casein for Zr4+, Fe3+, and Pd2+ affinity column was examined. The result shows that the resolution time (min) of the phosphonated casein 4 was higher than that of the dephosphated casein on the Zr4+ affinity column by liquid chromatography. However, the phosphonated casein and dephosphonated casein were not separated on the Fe3+ affinity column and Pd 21 affinity column by liquid chromatography. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 1250-1255, 2009