We report application of copper-mediated atom transfer radical polymerization in graft copolymerization of glycidyl methacrylate (GMA) from N-bromosulfonamide groups on polystyrene-divinyl benzene (PS-DVB) microspheres (210-420 mu m). The surface initiator groups were introduced by simple modification of crosslinked PS-DV-B (10% mol/mol) beads in three steps: (i) chlorosulfonation, (ii) sulfamidation with propylamine, and (iii) bromination. Initiation from surface-bound N-bromosulfonamide groups showed first-order kinetics (k = 1.04 x 10(-4) s(-1) in toluene at 70 degrees C) and gave poly(GMA) graft chains linked to the surface by hydrolytically stable sulfonamide bonds. High graft yields were attained (up to 294.4% within 21 h) while retaining the epoxy groups. Epoxy content of the resulting product (5.41 mmol g(-1)) revealed an average 17 GMA repeating units in the graft per initiation site. Taking advantage of the hydrolytic stability of sulfonamide linkages and well-known reactivity of the epoxy groups on dangling chains, "the hair-like structure" of the polymer beads prepared can be considered when devising more efficient functional polymers as catalysts or reagent carriers. (c) 2006 Wiley Periodicals, Inc.