AbstractCassia siamea seed polysaccharide was grafted with acrylonitrile under microwave (MW) irradiation without adding any radical initiator or catalyst. Free radicals are generated here due to the dielectric heating caused by the localized rotation of the hydroxyl groups at the polysaccharide backbone and initiate grafting. To obtain the optimal conditions for the microwave promoted grafting, effect of reaction variables such as monomer/seed gum concentration; MW power and exposure time on the graft copolymerization was studied and the maximum %grafting (%G) and %efficiency (%E) observed were 150% and 43.54%, respectively. The representative graft copolymer was characterized by Fourier transform‐infrared, Thermogravimetric analysis and X‐ray diffraction measurement, taking C. siamea gum as reference. At the same monomer concentration, K2S2O8/ascorbic acid initiated grafting onto the seed gum could result into 80% grafting with 23.22% efficiency. Various properties of the MW synthesized grafted gum like water/saline retention, water retention after saponification and viscosity of the gum solutions were studied. The results have been compared with the conventionally synthesized grafted gum and the parent gum. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2384–2390, 2006