Electrochemically generated base (EGB) was cathodically prepared from pyrrolidone, and it was used as an efficient base to generate an anion of methyl phenylacetate. The anion was oxidized by iodine to afford dimethyl 2,3-diphenylsuccinate in high yield and high dl selectivity. Optically active 2,3-diphenylsuccinic acid derivative was prepared by this EGB/iodine method. The oxidative homocoupling of methyl phenylacetate was also achieved with a catalytic amount of iodine by utilizing an electrochemical mediator system.