Electroinduced copolymerization of acrylonitrile (AN)-polyethylene glycol (PEG-400) initiated by Ce(IV) was performed in aqueous solution and compared with chemical copolymerization, which allowed Ce(III) to be converted to Ce(IV) electrochemically during the polymerization. The polymer that was insoluble in water was formed in the cathodic compartment. The effect of Ce(IV), H2SO4, monomer, PEG-400 concentration, temperature, time, and potential on the yield were studied and compared with similar effects under nonelectrolytic conditions. The role of Ce(IV) salt on the copolymerization was followed by spectrophotometric methods during the reaction period. Polymers were characterized by FTIR, UV-visible spectrophotometry, and NMR. Intrinsic viscosities of polymers were determined. Possible polymerization mechanisms are suggested in the case of electrolytic and nonelectrolytic conditions. The electrolytic process has a demonstrable advantage over the nonelectrolytic method.