The graft copolymerization of methyl methacrylate (MMA) onto mulberry silk fibers was studied in aqueous solution using the acetylacetonate oxovanadium (IV) complex. The rate of grafting was investigated by varying the concentration of the monomer and the complex, the acidity of the medium, the solvent composition of the reaction medium, the surfactants, and the inhibitors. The graft yield increases with increasing concentration of the initiator up to 8.75 × 10−5mol/L, of the monomer up to 0.5634 mol/L, and thereafter it decreases. Among the various vinyl monomers studied, MMA was found to be most suitable for grafting. Grafting increases with increasing concentration of HCIO4and with increasing temperature. Inhibitors like picryl chloride and hydroquinone significantly decrease the extent of grafting. Alcoholic solvents at a solvents/water ration of 10:90 seem to constitute the most favorable medium for grafting. A suitable reaction scheme has been proposed, and the activation energy calculated from the Arrhenius plots.