Vinyl acetate monomer was graft polymerized onto chitin with a redox initiator, cerium ammonium nitrate. Both the graft copolymerization and emulsion polymerization of pure poly(vinyl acetate) (PVAc) were observed during the reaction and a stable dispersion solution was obtained after the reaction. After the PVAc homopolymer was removed by acetone extraction, the grafting efficiency and grafting percentage were calculated from the weight balance. Transmission and scanning electronic microscope were used to observe the morphologies of the reaction product. Experimental results indicated that at initial stage of reaction, graft copolymerization, which occurred on the surface of chitin particles, dominated over the emulsion polymerization. After that, the rate of emulsion polymerization increased greatly and became dominant. The existence of chitin not only provided the stability of the emulsion particles, but also increased the polymerization rate. Structures of copolymers were evidenced with the techniques of Fourier transform infrared and differential scanning calorimeter.