A novel tactic to synthesize unsymmetrical 3-aryladipic acid esters has been developed via magnesium-promoted reductive coupling of ethyl cinnamates with methyl acrylate. In the present methodology, 3-aryladipic acid derivatives were prepared with good functional group tolerance and a wide substrate scope under very mild reaction conditions in good yields. The application of this reaction to dienic acid esters led to the successful control of the reaction to give 5-aryl-oct-3-enedioic acid esters with high regioselectivity.