The 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) mediated electrochemical oxidation of D-glucose to D-glucaric acid on a synthetically useful scale is reported. Using TEMPO and a graphite felt anode combined with a stainless steel cathode, D-glucose was oxidized under different conditions (pH, temperature, co-oxidant), and the reaction outcomes were analyzed. Optimized conditions for such oxidation are provided along with few new interesting results unique to this reaction, such as the appearance of a novel triacid. (C) 2009 Elsevier Ltd. All rights reserved.