AbstractThe ethylene glycol oxidation reaction on nickel and ruthenium modified palladium nanocatalysts was investigated with electrochemical, spectroelectrochemical, and chromatographic methods. These carbon‐supported materials, prepared by a revisited polyol approach, exhibited high activity towards the ethylene glycol electrooxidation in alkaline medium. Electrolysis coupled with high performance liquid chromatography/mass spectrometry (HPLC‐MS) and in situ Fourier transform infrared spectroscopy (FTIRS) measurements allowed us to determine the different compounds electrogenerated in the oxidative conversion of this two‐carbon molecule. High value‐added products such as oxalate, glyoxylate, and glycolate were identified in all electrolytic solutions, whereas glyoxylate was selectively formed at the Ru45@Pd55/C electrode surface. In situ FTIRS results also showed a decrease in the pH value in the thin layer near the electrode as a consequence of OH− consumption during the spectroelectrochemical experiments.