In this paper, oxidation of d-glucose on RuCl 2 (azpy) 2 (azpy=2-phenylazopyridine), as electrochemical mediator is studied. The complexes RuCl 2 (azpy) 2 were prepared according to literature procedures with some modifications. Two isomers (E–Z or γ-RuCl 2 (azpy) 2 and E–E or δ-RuCl 2 (azpy) 2 ) were isolated. Each isomer and the crude were investigated electrochemically by immobilizing them with a Nafion/water solution on carbon Toray (CT) as supporting electrode. The voltammetric investigations were in fact used to determine the optimized oxidation potentials, which were helpful to carry out long-term electrolyses of glucose in carbonate buffer. High value products such as 2-ketogluconic and gluconic acids were obtained. The comparison of the results between the crude complex and the two isomers showed that γ-RuCl 2 (azpy) 2 was the most active catalyst.