Nuclear magnetic resonance spectroscopy was used to investigate the position of active centers in polyamide fibers subjected to graft copolymerization with poly(acrylic acid), poly(itaconic acid), and poly(2-vinylpyridine) initiated by thermal oxidation in air. As a result, structural changes in polyamide fibers brought about by oxidation and subsequent grafting of the above mentioned polymers were observed. It was estimated that the generation of active centers that initiate the copolymerization take place at the nitrogen atoms of the amide groups in the polyamide chain. This was confirmed by the broadening of the absorption band for the methylene group adjacent to the nitrogen as well as by the absence of a new absorption band for the methine groups, assuming that the generation of active centers and grafting would take place at the carbon atom of the methylene group in position a to the amide group.