The graft mechanism of acrylonitrile (AN) onto starch under the initiation of potassium permanganate was investigated. The relationships of the grafting rate and the concentrations of potassium permanganate, AN, and backbone starch, as well as the reaction temperature, were established. On this basis, the equation for the rate of the graft copolymerization was derived, and the apparent activation energy for the graft copolymerization was obtained. Through the study of the oxidation reaction of starch with manganic ions, the valence changes of manganic ions during the graft copolymerization, and the grafting ability of different starch derivatives, together with electron spin resonance analysis, the grafting mechanism for the graft copolymerization of AN onto starch under the initiation of potassium permanganate was determined. (C) 2003 Wiley Periodicals, Inc.