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 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 the electrolytic solutions, while glyoxylate was selectively formed at the Ru45@Pd55/C electrode surface. In situ FTIRS results also showed a decrease of the pH value in the thin layer near the electrode as a consequence of OH- consumption during the spectroelectrochemical experiments.