Nickel–molybdenum (Ni–Mo) materials are widely used functional oxide catalysts for the hydrogen evolution reaction. In this work, we investigate the high activity of Ni–Mo by depositing size-controlled Ni nanocrystals (NCs) onto Mo substrates. We observe a synergistic increase in catalytic activity that does not scale with the Ni–Mo interface length. This evidence points to a bulk electronic interaction of the two metals that is separate from the mechanism of enhancement seen in conventionally co-deposited Ni–Mo electrocatalysts. In addition to elucidating the catalytic behavior of the Ni–Mo system, this work offers a general NC-based paradigm for investigating fundamental interactions and synergistic effects in electrocatalytic materials.