Graft copolymerization of low‐density polyethylene (LDPE) onto starch was carried out with glucose–cerium(IV) redox initiator in an aqueous sulfuric acid medium under nitrogen atmosphere. The graft yield was influenced by various parameters like reaction time, temperature, and concentrations of acid, glucose, polyethylene (PE), starch, and initiator. A maximum graft yield of 85.66% was obtained at a temperature of 50°C and at higher concentration of starch. Effect of grafting on crystallinity, morphology, and thermal properties of modified PE has been evaluated using X‐ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA/DTA). Biodegradability of starch‐grafted PE has been tested applying soil‐burial test. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3229–3239, 2006