Hydrogen (H 2 ) is well-known for its potential to become the future fuel and bring a more sustainable energy system [1] . The selective electrooxidation of organic compounds from biomass appears to be a possible substitute for the kinetically slow oxygen evolution reaction (OER) at the anode, which increases the electrical energy input for a conventional water electrolysis in alkaline media [2] . However, this approach is currently impeded by limited fundamental knowledge of the different active sites of electrocatalysts. The latter can be used to control selectivity at low potential and high current density to co-generate value-added products at the anode instead of CO 2 by complete oxidation. Nanostructured gold-based multi-metal electrocatalysts can meet such objectives. Particularly in the electro-valorization of cellulosic biomass at electrode potentials unfavorable to C-C bond breaking and high overall cell voltage. To develop such electrocatalysts, we have initiated a multivariate methodology to study