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The present paper reports cyclic voltammetric and a.c. impedance spectroscopy investigations on the influence of the acetonitrile concentration on the kinetics (and individual product’s efficiency) of the ethanol oxidation reaction (EOR), performed on a polycrystalline Pt electrode surface in 0.5 M H₂SO₄ and 0.1 M NaOH supporting solutions. The kinetics of the EOR were examined at room temperature over the voltammetric potential range, which covers the electrooxidation of surface-adsorbed CO_Ads species, as well as the formation of acetaldehyde molecules. In addition, the time-dependent efficiency of acetate and acetaldehyde formation in relation to the initial acetonitrile content for both acidic and alkaline electrolytes was evaluated by means of spectrophotometric Ultraviolet/ Visible Spectroscopy (UV-VIS) instrumental analysis.