Recent computational studies have proven valuable in rationalizing the ECH of organic compounds on Pd systems based on the binding of key reaction intermediates. However, to the best of our knowledge, the influence of the electrode surface coverage on the ECH activity/selectivity has not yet been reported in the literature. We believe this knowledge is critical to rationally design high-performance ECH electrocatalysts based on earth-abundant elements, which explains why such materials have remained elusive. Herein, we report a bottom-up approach for designing non-precious metal cathodes for the selective ECH of organic substrates. Computational investigations of the density and binding strength of H surface coverages on different transition metals under relevant ECH conditions have identified Cu, Au, and Ag as promising electrocatalysts. These theoretical predictions are experimentally demonstrated for the ECH of acetophenone (AP) to 1-phenylethanol (1-PEA) on Ag, Au and Cu electrodes, achieving FEs and yields up to 90% at low applied potentials (ca. -0.5 VRHE) and in alkaline media. Notably, these cathodes outperform other transition metals tested in this work by at least one order of magnitude in terms of FEs and yields, including In, Ni, and even the precious Pt metal, which is deemed as a state-of-the-art ECH electrocatalyst (Fig. ). In addition, experimental studies show that this bottom-up approach may be generalized to other organic unsaturated substrates featuring C=O, C=C, C≡C, and C≡N bonds, obtaining remarkable yields (70-90%) from ECH on a Cu electrode. Overall, this work highlights the importance of H surface coverages in ECH processes and how this knowledge can be leveraged to tailor non-noble metal cathodes to sustainably produce chemical feedstocks and added-value products.