An electrochemical method for the direct synthesis of 1,2-diester derivatives from abundant and readily available olefins and carboxylic acids is described. The method is applicable to a variety of aromatic/aliphatic olefins and (hetero) aromatic/aliphatic carboxylic acids to produce the corresponding 1,2-diesters in moderate to good yields under mild and environmentally friendly conditions without the need for metals, catalysts, oxidants, sacrificial reagents and additives. The only by-product of the reaction is hydrogen released at the cathode, so this method is clean and highly atom- and step-economical. The diesterification of drugs and natural products further demonstrates the synthetic utility of the method.