While alkaline electrolysis can minimize the competing HER, the electrode surface under these conditions might still be able to dissociate water to source the H atoms needed for ECH. Therefore, we posited that an ideal ECH catalyst should promote water dissociation in an alkaline media, retaining the H atoms as distant as possible to minimize HER and with moderate binding strength to facilitate the ECH of organic substrates. To identify cathode materials that satisfy these premises, we performed periodic density functional theory (DFT) calculations on several transition metals, namely Ag, Au, Cu, Ni, and In (see details in Supplementary Materials). These elements were chosen as they display a wide range of H binding energies at reducing potentials based on previous theoretical studies on HER. For comparison, we also included Pt in our investigations as it is regarded as a state-of-the-art ECH electrocatalyst. For each metal, the relative Gibbs adsorption energies (ΔGi) of different surface terminations with varying concentrations of *H, *OH, and *O species (* denotes a surface metal site) were investigated as a function of the applied potential. The results of this analysis are illustrated in the surface diagrams depicted in Fig. , which reveal that *OH and *O coverages (orange/red lines) are favored at positive (oxidizing) potentials, while *H coverages (blue lines) are favored at negative (reducing) potentials, as expected. Accordingly, in the potential window commonly used in ECH studies (i.e. from 0 to -1.0 VRHE), we predict the metals to present different concentrations of adsorbed H atoms. We also note that the calculated ΔGH (in eV) at 0 VRHE for one H atom adsorbed on the different metals follows the trend: In (+0.90) > Ag (+0.64) ~ Au (+0.64) > Cu (+0.25) > Ni (-0.12) ~ Pt (-0.09). These values, besides being a good description for the HER, can be taken as an indication of the thermodynamic driving force towards water dissociation. More specifically, very positive values of ΔGH imply a lack of surface H atoms available for ECH (e.g. In displays the highest ΔGH value, and therefore its surface is predicted to be bare), whereas negative values are expected to favor water dissociation, although they may also hinder ECH since the H transfer to the substrate would become energetically demanding. In light of these computational data, and the fact that ΔGH shifts by -eU with the applied potential U according to the computational hydrogen electrode model, we hypothesized Cu, Ag and Au to be good candidates to promote the ECH of organic substrates in alkaline media at relatively low potentials by sourcing H atoms from the surface coverage.