In this article, the graft copolymerization of 4-vinyl pyridine onto poly (ethylene terephthalate)(PET) via the potassium diperiodacuprate(III)–PET redox system as an initiator was investigated in an alkaline medium. The graft copolymer was characterized with Fourier-transform infrared spectra analysis. A mechanism is proposed to explain the generation of radicals and the initiation. The effects of reaction variables, such as the initiator concentration, the ratio of monomer to PET, pH, and reaction temperature and time, are investigated, and the grafting conditions are optimized. Graft copolymers with high grafting efficiency are obtained, thus indicating that potassium diperiodacuprate(III)-PET redox system is an efficient initiator for this graft copolymerization. The quaternized PET-g-PVP (QPEVP) is proved to be an excellent adsorbent to heavy metal ions.