The Glycerol electrooxidation reaction (GEOR) was investigated on nickel electrode in alkaline media following a sinusoidal-wave treatment in a solution of 0.1 M Na2SO4 + 30 mM ascorbic acid. This treatment significantly increased the catalytic activity of Ni towards the GEOR. The electrochemical active surface area showed a six-fold increase, while the current density of glycerol oxidation was enhanced over nine times with a concurrent onset potential decrease by 45 mV. SEM analysis before and after the treatment revealed some morphology changes through the formation of additional grooves and pits on the Ni surface. XPS confirmed that before the treatment, the surface consists of Ni metal in addition to NiO, Ni(OH)2 and NiOOH, whereas after the treatment, 97% of the surface is Ni hydr'oxide composed of Ni2+ and Ni3+. Chronoamperommetry coupled with in-situ polarization modulation infrared-reflection absorption spectroscopy (PM-IRRAS) for simultaneous analysis of products on the Ni surface and in the bulk solution showed that the main reaction products on both untreated and treated Ni surfaces are glyceraldehyde, carbonyl, carboxylate ions and some carbon dioxide. (C) 2017 Elsevier B.V. All rights reserved.