Acetoin could shortly become a platform molecule due to current progress in fermentation technology, the megatrend for shifting from an oil-based economy to the one based on biomass, the quest for green manufacturing processes and its two highly reactive carbonyl and hydroxyl moieties. In this paper, the successful electro-conversion of acetoin into two valuable chemicals, 2,3-butanediol (2,3-BD) and methyl ethyl ketone (MEK), at a constant electrical current in an aqueous phase at room temperature using both divided and undivided 20 cm2 filter-press flow cells under experimental conditions suitable for industrial production is reported. Cathode material is the key parameter to drive the electroreduction towards one or another chemical. 2,3-BD is the major chemical produced by electrohydrogenation when low hydrogen overvoltage cathodes, such as Pt and Ni, of high surface areas obtained by PVD coating on a carbon gas diffusion layer are used, while MEK is the principal product produced by electrohydrogenolysis when high hydrogen overvoltage cathodes, such as graphite, Pb and Cd foils, are employed. 2,3-BD and MEK can be obtained, respectively, in 92.8% and 85.7% selectivities, 71.7% and 80.4% current efficiencies, with 1.21 and 1.08 kg h−1 m−2 productivities and power consumptions of 2.94 and 4.1 kWh kg−1 using undivided cells and aqueous K2HPO4 electrolysis media at pH values of 3.6 and 5.5. The reported electroconversion of acetoin is highly flexible because 2,3-BD and MEK can be produced by changing just the cathode but using the same cell, with the same electrolyte at the same current density.