Herein,we describe an environmentally benign and cost-effective protocol for the synthesis of valuable bifuranyl dicarboxylates,starting with α-bromination of readily accessible furan-2-carboxylates by LiBr and K2S2O8.Furthermore,the bromination intermediate product 5-bromofuran-2-carboxylates were then conducted in a palladium-catalyzed reductive homocoupling reactions in the pres-ence of alcohols to afford bifuranyl dicarboxylates.One of the final products in this protocol,[2,2’]bifuran-5,5’-dicarboxylic acid es-ters,are essential monomers of poly(ethylene bifuranoate),which can be served as an green and versatile alternative polymer for traditional poly(ethylene terephthalate)that is currently common in technical plastics.