Furfural (FF) is a biomass-derived oxygenate and a platform chemical that can produce a biofuel candidate, 2-methyl furan (MF), and valuable chemicals by hydrogenation and hydrogenolysis. Electrochemical hydrogenation and hydrogenolysis (ECH) is a promising method for upgrading of FF to produce MF and valuable chemicals such as furfuryl alcohol (FA). The production rate, selectivity and faradaic efficiency (FE) of products on microcrystalline and nanocrystalline Cu electrodes were compared with a bare Cu electrode at different potentials. At near onset potentials of ECH of FF, the production rate of FA + MF on nanocrystalline Cu was 2.4 times that of bare Cu, with a negligible amount of side product, hydrogen gas. As the magnitude of applied potential increased to much beyond the onset potential, the production rate for FA + MF more than doubled on the nanocrystalline Cu catalyst compared to bare Cu, when a significant quantity of FF was present. The nanocrystalline Cu catalyst also maintained stable and repeatable FE and production rate for desired products during repeated cycles of ECH of FF.