Poly (methyl methacrylate) (PMMA) is successfully grafted onto cellulose in homogeneous medium in N,N-dimethyl acetamide/LiCl solvent system. The method is based upon ring opening reaction of cellulose with Ce4+ ion. Ceric ammonium nitrate (CAN) forms free radical on cellulose back bone in presence of DMSO via ring opening mechanism and PMMA is grafted through homogeneous breaking of the acrylic double bond. Methylene blue was used as an inhibitor to check the formation of homopolymer. The graft yield and grafting efficiency was studied by varying reaction time, temperature, and monomer concentration. The products are characterized by FTIR and H-1-NMR analysis and a possible reaction mechanism is deduced. Thermal degradation of the grafted products is also studied by thermo-gravimetric analysis (TG).