Herein, a comparative analysis of two case example catalysts for electrocatalytic hydrogenation (ECH) of furfural under acidic conditions, namely a copper polycrystalline disc and copper nanoparticles dispersed on carbon support, is performed. To gain a detailed insight on ECH trends, a task-specific methodology is employed based on electrochemistry–mass spectrometry coupling, which enabled time- and potential-resolved detection of volatile ECH products, i.e., 2-methylfurane (2-MF) and H2. In this way, the ability to elucidate potential-dependent product distribution for the two catalysts, namely faradaic efficiency, is achieved. Accordingly, the nanoparticulate analog is significantly more active toward competitive hydrogen evolution reaction and 2-MF production, whereas the polycrystalline sample is more selective toward furfuryl alcohol. The observed differences in ECH are ascribed to alterations in surface domains, which is supported by surface-sensitive lead underpotential deposition characterization.