Electrochemical valorization of non-food biomass-derived carboxylates into fuels is promising for the conversion, storage, and distribution of renewable electricity. Herein, we demonstrate that biofuels, hydrogen, and bicarbonate can be simultaneously produced in an electrochemical cell by one-step electrolysis of free fatty acids under ambient conditions on 3D self-supported ultralow Pt loading (2 wt %) electrode. The three valuable products can naturally separate from each other during the electrolysis in the alkaline aqueous solution. The experimental suggests that Pt(100) and Pt(110) are favorable for the production of non-Kolbe and Kolbe hydrocarbons, respectively. DFT calculation further clarifies the adsorption and stabilization of the reaction intermediates on Pt(100) and Pt(110). © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim