Electrochemical hydrogenation of unsaturated hydrocarbons, when powered by renewables, represents a unique opportunity to substitute current energy-intensive synthetic routes. Modulation of adsorption energies of the organic substrate and key intermediates of the reaction is critical for fine tuning of the yield, selectivity and kinetics of the reaction. Interestingly, mounting evidences exist regarding the role of electrolyte composition on the outcome of semi-hydrogenation reactions. Nevertheless, electrolyte optimization is a complex task, owing to its hybrid nature. Indeed, it is composed of water serving as proton source, an organic solvent necessary to dissolve the organic substrate and a conducting salt. Herein, we demonstrate that varying conducting salt and organic solvent have a dramatic impact on the outcomes of semi-hydrogenation of alkynes. By varying salt and water concentration, we demonstrate that water does not serve as proton source, and instead addition of an acid is necessary. While increasing acid concentration increases the yield of the reaction, at too large concentrations hydrogen evolution reaction becomes predominant. Furthermore, combining electrochemical measurements with spectroscopic techniques including Fourier transform infrared (FTIR) spectroscopy and small angle X-ray spectroscopy (SAXS), we demonstrate that the electrolyte solvation structure dramatically impacts the yield of the reaction. Organic solvents weakly interacting with water, including acetonitrile, form aqueous nanoheterogeneities that prevent the organic substrate from accessing the catalyst interface and thus lead to limited yields. Instead, solvents such as dimethylformamide form homogeneous mixtures with which all reactants can access the interface, leading to yields greater than 80% for optimized compositions.