In this article, we have used the potassium persulfate to initiate the graft copolymerization of methyl methacrylate onto cellulosic biofibers in aqueous medium. Different reaction parameters, such as reaction time, initiator molar ratio, monomer concentration, amount of solvent, and reaction temperature, were optimized to get the maximum percentage of grafting (50.93%). The graft copolymers thus formed were characterized by Fourier transform infrared, scanning electron microscopy, X-ray diffraction, and thermogravimetric, differential thermal analysis, and derivative thermogravimetric techniques. A mechanism is proposed to explain the generation of radicals and the initiation of graft copolymerization reactions. On grafting, percentage crystallinity decreases with reduction in its stiffness and hardness. The effect of grafting percentage on the physicochemical properties of raw as well as grafted fibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.