Electrocatalytic hydrogenation of lignocellulosic bio-oil to value-added chemicals offers an attractive avenue to use the increasing intermittent renewable electricity and biomass-derived feedstocks. However, to date the partial current densities to target products of these reactions are lower than those needed for industrial-scale productivity, which limits its prospects. Here we report a flow-cell system equipped with a Rh diffusion electrode to hydrogenate lignocellulose-derived aromatic monomers, such as furans and lignin monomers, to value-added chemicals. We achieve high faradaic efficiencies up to 64% at industrial-scale current densities of 300–500 mA cm−2, representing high productivities to target products. A screening of electrocatalysts indicates that only by highly-electrolyte-permeable Rh diffusion electrodes are we able to unite current density with faradaic efficiency. We apply in-situ infrared reflection–absorption spectroscopy to investigate the electrode-potential-dependent reaction pathways and intermediates, confirming a wide potential window for efficient electrocatalytic hydrogenation of lignocellulose-derived aromatics to target products.