In summary, this work reports the computationally-guided design of non-precious metals for the selective ECH of unsaturated organic substrates in alkaline media. This is achieved by tailoring the density and binding strength of H coverages on the electrode surface and by establishing a series of catalyst design principles. In particular, metal cathodes are chosen to promote water dissociation and reduce the generated protons to H atoms, while retaining them on the electrode surface with moderate strength to facilitate ECH. In addition, metals displaying well-dispersed H atoms on the surface are desirable to prevent HER via a Volmer-Heyrovsky mechanism. With these premises, DFT calculations identify Cu, Au, and Ag as promising ECH electrocatalysts. Experimental studies confirm the excellent performance of these metals for the selective ECH of acetophenone (AP) to 1-phenylethanol (1-PEA) in alkaline media, attaining FEs and yields up to 90% at ca. -0.5 VRHE. Notably, these cathodes outperform other transition metals investigated in this work by at least one order of magnitude in terms of FEs and yields, including In, Ni, as well as the state-of-the-art and precious Pt metal. This novel bottom-up approach of tailoring H surface coverages is further demonstrated with the successful ECH of a broad scope of unsaturated organics featuring C=O, C=C, C≡C, and C≡N bonds with moderate to excellent conversions and chemoselectivities (70-90%) on a Cu electrode. Overall, this work highlights the critical role of H surface coverages and how this knowledge can be leveraged to tailor high-performance ECH catalysts based on earth-abundant metals. Hence, this strategy is envisioned to pave the way for the rational design ECH catalysts to electrify the synthesis of chemical feedstocks and added-value products, thus contributing to reduce the carbon footprint of chemical industry.