A paired electrooxidative method has been developed to synthesize D-arabinose in a divided cell. D-arabinose is a material which has an important role in the production of vitamin B2 and DNA. Sodium gluconate was directly oxidized at the anode and indirectly oxidized in the catholyte by bubbling oxygen which was reduced to H2O2 and OH. free radicals. In the catholyte, indirect oxidation of sodium gluconate was mediated by Fe3+ and OH. free radicals. The optimal current efficiencies for D-arabinose production in the anolyte and catholyte were found to be 88.37% and 39.12%, respectively, and the total current efficiency of the paired electrooxidation was 127.49%. The paired electrosynthesis of D-arabinose is more economical in terms of power consumption than electrosynthesis that employ a single anode or cathode as the working electrode. The influence of cathodic/anodic CV and I/E curves, redox mediators and the amount of charge passed were also examined.