The anthropogenic emissions of CO2 since the industrial revolution, in part by numerous industrial chemical processes that rely on reagents produced from fossil fuels, has already left an enduring effect on the Earth's environment and climate.(1) Defossilization of our economy can be supported through the electrification of industrial synthetic processes by coupling electrosynthesis with renewable energy sources. For example, electrochemical hydrogenation (ECH) of organic substrates has emerged as a promising strategy to synthesize organics and valorize biomass derivatives to produce valuable fine chemicals, natural products, and medicines. Furthermore, if driven by renewable electricity under mild conditions, ECH could supersede traditional thermal hydrogenation processes, which typically demand highly pure H2 produced from steam reforming, as well as high pressures and elevated temperatures. Organic ECH reactions for a series of functional groups have been reported, including C=O, C=C, C≡C and C≡N (Fig ).(15-28) However, these systems typically rely on precious metal catalysts, such as Pt and Pd. Moreover, in aqueous media, these cathode materials face the competition with the more facile hydrogen evolution reaction (HER), which usually requires less negative potentials, compromising the Faradaic efficiency (FE) towards the target ECH products. One strategy to minimize the competing HER is to work in alkaline media, wherein the concentration of protons is much lower.(31) A notable example is the ECH of acetonitrile, where a FE of 80-90% was achieved at 100-500 mA cm -2 in 1 M aqueous NaOH, in contrast to the dominant HER under acidic or neutral conditions. While hindering HER to the advantage of ECH reactions, the use of alkaline electrolytes poses important requirements due to the change in the sourcing hydrogen under these conditions: ECH sources H atoms from protons present in the acidic electrolyte, whereas H atoms are mainly sourced through water dissociation on the electrode surface in alkaline solution (Fig ). In addition, the adsorbed H atoms must exhibit a moderate binding strength at the operating applied potential in order to facilitate the ECH of the organic substrate, according to the Sabatier's principle. Hence, we envisioned the presence of a surface coverage of moderately bound H atoms to be crucial to effectively promote ECH in alkaline media while minimizing the competing HER.