The electrochemical deposition of Cu nanoparticles with an average diameter of approximately 25-35 nm has been reported at liquid-liquid interfaces by using the organic-phase electron-donor decamethylferrocene (DMFc). The electrodeposited Cu nanoparticles display excellent catalytic activity for the hydrogen evolution reaction (HER); this is the first reported catalytic effect of Cu nanoparticles at liquid-liquid interfaces.