Graft copolymerization of 4-vinyl pyridine (4-VP) on poly(ethylene terephthalate) (PET) films using a benzoylperoxide (Bz(2)O(2)) initiator was investigated under different conditions including polymerization time, temperature, monomer concentration, and initiator concentration. Dimethyl sulfoxide (DMSO) was used as swelling agent to promote the incorporation and the subsequent polymerization of 4-VP to PET films. Maximum percent grafting was obtained when the polymerization was carried for a period of two hours at 65 degrees C. Increasing the monomer concentration from 0.2M to 0.8M and Bz(2)O(2) concentration from 1.0 X 10(-3)M to 2.5 X 10(-3)M was accompanied by a significant enhancement in percent grafting. Monomer diffusion on PET films and its effect on the grafting yield were studied and intrinsic viscosities of grafted films were also measured. (C) 1996 John Wiley & Sons, Inc.