Electroreduction of aliphatic esters in THF was found to be promoted by the catalytic amount of porphine-magnesium(II) complexes and afforded 2-alkoxytetrahydrofuran derivatives, the coupling products between alkoxide anions formed by the electroreduction of aliphatic esters and THF cation generated by the anodic oxidation of the solvent (THF). In this reaction, chlorophyll a extracted from Trifolium repens L was remarkably effective. In addition, lanthanide metal(III) ions such as samarium trichloride were also found to be effective for the electroreduction of aliphatic esters.