Polymerization of acrylamide (AA) has been studied in aqueous solution in the presence of a Ce(IV) salt-oxalic acid initiator system in an electrochemical cell with and without separation of anolyte and catholyte. For reactions that required the cathode and anode sections to be analyzed individually, a cell whose compartments were divided by a sintered glass disk of the medium porosity was employed. Polymerization was initiated by a free radical that is formed by the fast reaction of oxalic acid and Ce(TV). The electrolysis of the reaction solution results in regeneration of Ce(IV), which can oxidize oxalic acid to produce radicals. The effect of sulfuric acid and cerium (IV) salt concentration and temperature on the yield of electroinitiated polymerization in different cell designs and structural identification of products were performed. Reaction was also followed by cyclic voltametric measurements, and a mechanism was proposed. Results indicated that the electrolysis method with a divided cell (85% conversion) shows advantages, compared with nonelectrolytic (5% conversion) and with undivided electrochemical cell (25% conversion) methods where a high concentration of initiator was used.