Biomass electro-oxidation is a promising approach for the sustainable generation of H2 by electrolysis with simultaneous synthesis of value-added chemicals. In this work, the electro-oxidation of two structurally different organic hydroxyacids, lactic acid and gluconic acid, was studied comparatively to understand how the chemical structure of the hydroxyacid affects the electrochemical reactivity under various conditions. It was concluded that hydroxyacids such as gluconic acid, with a considerable density of C−OH groups, are highly reactive and promising for the sustainable generation of H2 by electrolysis at low potentials and high conversion rates (less than −0.15 V vs. Hg/HgO at 400 mA cm−2) but with low selectivity to specific final products. In contrast, the lower reactivity of lactic acid did not enable H2 generation at very high conversion rates (<100 mA cm−2), but the reaction was significantly more selective (64 % to pyruvic acid). This work shows the potential of biomass-based organic hydroxyacids for sustainable generation of H2 and highlights the importance of the chemical structure on the reactivity and selectivity of the electro-oxidation reactions.