Acetonitrile, an abundant byproduct of the Sohio process for acrylonitrile synthesis, presents an attractive feedstock for electrocatalytic transformation into value-added chemicals. Here, we report the selective electrochemical reduction of acetonitrile to ethylamine—a key intermediate in pharmaceuticals and agrochemicals—using oxide-derived copper nanowires (OD-CuNWs). We identified acetamide—a previously overlooked product of acetonitrile electroreduction—as a by-product that forms via a thermocatalytic route. This competing pathway was found to depend on operational parameters, including temperature, pH, and the nature of the electrolyte. Specifically, an alkaline environment (pH > 10) and the temperature rise favours acetamide pathway. Leveraging mechanistic insights to guide reaction condition optimization, we achieved 80% Faradaic efficiency toward ethylamine at a high current density of 410 mA cm −2 by suppressing competing acetamide and hydrogen formation pathways. The OD-CuNW catalyst exhibits high stability over multiple cycles, maintaining both activity and selectivity. These findings provide mechanistic insight and practical guidance for optimizing acetonitrile electroreduction toward sustainable ethylamine synthesis.