The kinetics of polymerization of acrylonitrile initiated by the redox systems cyanoacetic acid/Mn(OAc)3 and cyanoacetic acid/tris(benzoylacetonato)manganese(III) in dimethylsulphoxide as solvent have been investigated over the range 20-35°. The kinetics of oxidation are consistent with the formation of intermediate complexes between the reactants, followed by electron transfer. Manganous ions inhibit the reaction by competitive complexation. The primary radicals are very efficient as initiators of polymerization which is terminated by mutual interaction of macroradicals. Mechanisms have been proposed to explain the kinetics; rate and equilibrium constants have been evaluated. © 1982.