Technical Abstract: Modified starch-based polymers can be engineered for specific properties by combining starch with synthetic polymers through graft copolymerization. Polyacrylamide grafted starch have received a great deal of applications in areas such as superabsorbent paper-making additives, drag reduction and textile sizing. So far there are over a hundred papers and tens of patents issued for graft copolymerization. All of these used oxidants such as ceric ammonium nitrate or ammonium persulfate as catalyst. We would like to report a process where we replaced the inorganic oxidants by a nature¿s catalyst HRP enzyme. At room temperature and in water HRP/H2O2/2,4 pentanedione catalyzed free radical grafting of acrylamide onto starch gave starch-polyacrylamide graft copolymers with M. Wt in the range of 100-200K with good product recovery and a grafting efficiency of 33-65%. HRP is shown to be a viable alternative to conventional inorganic free radical catalysts. Starch-polyacrylamide graft copolymers was synthesized by the enzymatic oxidative polymerization of acrylamide and starch using HRP catalyst, H2O2 and pentadione in water and phosphate buffer. We discovered a process where we replaced the inorganic oxidants by a nature¿s catalyst HRP enzyme. We have developed a enzyme catalyzed novel green pathway to starch-polyacrylamide graft copolymers. Our discovery will help the starch graft copolymers manufacturers to avoid the use of pollutant such as cerric ammonium nitrate.