Electrochemical oxidation of the primary and the anomeric hydroxy group in sugars is welldescribed. TEMPO and 4-acetamido-TEMPO are the mediators of choice, and Pt and Au based electrodes have mainly been applied. Similar results were obtained under heterogeneous conditions, in which a TEMPO immobilized Nafion perfluorinated film was deposited onto graphite electrodes. As electrochemical, quinuclidine-mediated oxidation of glycosides had not been studied, we started by adopting the reaction conditions of Baran et al., and subjected methyl-α-Dglucopyranoside (1) to electrolysis with RVC (anode) and Ni foam (cathode) electrodes.