Aqueous polymerization of acrylonitrile initiated by the Ce(IV)-DMSO redox system was studied in the temperature range of 40°-60°C. The rate of polymerizationRpwas found to be approximately proportional to [M]3/2within the range of monomer concentration of 0.32–1.2 mL-1. Effects of time and concentration of Ce(IV), DMSO, H2SO4, and salts were studied. The overall activation energy for the polymerization reaction was estimated to be 4.606 kcal/mol. A suitable kinetic scheme was proposed in the light of these experimental results. Kinetic analysis shows that the mutual termination predominates over linear termination.