The adsorption and electrooxidation pathways of ethylene glycol (EG) on polycrystalline palladium surfaces have been investigated in both alkaline and acidic media by in situ FTIR spectroscopy in conjunction with cyclic voltammetry. Palladium exhibits a high electrocatalytic activity in alkaline solution with low onset oxidation potentials and high current densities, depending on the pH, as well as on the supporting electrolyte. Higher potentials are required for EG oxidation in acidic solutions, where the catalytic performance decreases with increasing the pH. The products and intermediates of EG oxidation on Pd are influenced by the pH. In alkaline media, both C(2) species (glycolate, glyoxal, glyoxylate and oxalate) and C(1) species (formate and carbonate) are formed in mutual concentrations depending on the pH. In contrast, CO(2) is selectively produced in acidic aqueous solution.