Graft reaction of acrylamide (AM) and 4-vinyl pyridine (4-VP) onto ultra-low molecular weight poly(vinyl alcohol) by ceric (IV) ion initiation had been systematically investigated; and the graft conditions were optimized by studying the effect of monomer/initiator concentration, solvents composition, reaction time and temperature. At optimized conditions, the maximum grafting efficiency and grafting ratio was similar to 50% and 51%, respectively with the presence of AM, whereas they decreased to 19% and 23%, respectively, without the presence of AM. Thermogravimetric analysis showed that as-resulted graft copolymer had a lower thermal stability than homopolymer PVA. FTIR and H-1-NMR confirmed chemical structure of as-synthesized graft copolymer. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 3954-3962, 2009