The graft copolymerization of 4-vinyl pyridine (4VP) onto nylon-6 (PA6) was studied by using potassium diperiodatonickelate(IV) (DPN)-PA6 redox system in alkaline medium. The structures of graft copolymers were confirmed by Fourier transfer infrared spectroscopy (FTIR) and X-ray diffraction. The properties of graft copolymers were investigated by thermogravimetric analysis (TGA). A mechanism was proposed to explain the generation of radicals and the initiation. The effects of reaction variables, such as the initiator concentration, the ratio of 4VP to PA6, pH as well as reaction temperature and time were investigated. Graft copolymers with high grafting efficiency (>95%) were obtained, which indicated that DPN-PA6 redox system is an efficient initiator for this graft copolymerization. The quaternized PA6-g-P4VP (QPAVP) was proved to be an excellent adsorbent to heavy metal ions.