A series of graft Copolymers poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl-co-ethylene oxide)-graft-polystyrene or poly(tert-butyl acrylate) [poly(GTEMPO-co-EO)-g-PS/PtBA] were synthesized by atom transfer nitroxide radical Coupling (ATNRC) chemistry. Linear precursor copolymers with multipending 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) groups [poly(GTEMPO-co-EO)] were prepared first by anionic ring-opening copolymerization of 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (GTEMPO) and ethylene oxide (EO), and then polystyrene (PS) and poly(tert-butyl acrylate) (PtBA) with bromide end group were obtained by atom transfer radical polymerization (ATRP) using ethyl 2-bromoisobutyrate (EBiB) as the initiator and CuBr/ N,N,N',N',N ''-pentamethyidiethylenetriamine (PMDETA) as catalyst. When the linear precursor copolymer poly(GTEMPO-co-EO) was mixed with PS or PtBA chains and heated to 90 degrees C in the presence of CuBr/PMDETA, the formed secondary carbon radicals at the PS or PtBA chain ends were quickly trapped by the nitroxide radicals on poly(GTEMPO-co-EO) main chain to form graft copolymer in which the alkoxyamines were at the conjunction points. The efficiency of coupling reaction was in the range of 90.2-95.9% for PS and 82.3-88.4% for PtBA when their number average of molecular weight M-n was in the range of 1500-7800 g/mol and ratio of GTEMPO/ EO in copolyrner was 1:21.